Bulletin of the Chemical Society of Japan

Vol. 69, No. 08 (August, 1996)

RETRUN to the front page

Copyright (C) 1996 by The Chemical Society of Japan


CONTENTS


=============================
Accounts
=============================

Endohedral Metallofullerenes: New Spherical Cage Molecules with Interesting Properties

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Shigeru Nagase,* Kaoru Kobayashi, and Takeshi Akasaka

pages 2131-2142



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Headline Articles
=============================

Biological Activity of Water-Soluble Fullerenes. Structural Dependence of DNA Cleavage, Cytotoxicity, and Enzyme Inhibitory Activities Including HIV-Protease Inhibition

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Eiichi Nakamura,* Hidetoshi Tokuyama, Shigeru Yamago, Takashi Shiraki, and Yukio Sugiura*,

pages 2143-2151



=============================
Articles
General and Physical
=============================

The Study of the Electron-Positron Pair in CS2

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Tetsuya Hirade

pages 2153-2157


Electrochemical Reduction of N2 O on Gas-Diffusion Electrodes

GO TO the graphical abstract

Nozomi Konishi, Kohjiro Hara, Akihiko Kudo, and Tadayoshi Sakata*

pages 2159-2162


Inclusion Complexation of 4-Biphenylcarboxylate, 4-Biphenylacetate, and 4-Biphenylsulfonate with -Cyclodextrin, Studied by Pulse Radiolysis

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Yukio Yamamoto,* Yoichi Yoshida, and Seiichi Tagawa

pages 2163-2166


Photoinduced Electron Transfer from Cyclic Organogermanium Compounds to C60 Studied by Laser Flash Photolysis

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Osamu Ito,* Yoshiko Sasaki, Akira Watanabe, and Kunio Mochida

pages 2167-2171


A Simple New Method for Determining Diffusion Coefficients of Interacting Particles in Porous Silica and Gels

GO TO the graphical abstract

Shigeo Sasaki* and Hiroshi Maeda

pages 2173-2178


Hydration and Pressure Effects on the Inter- and Intramolecular Vibrations of Tetramethylpyrazine Crystals

GO TO the graphical abstract

Masayoshi Maehara, Yoshio Suzuki, Hideki Mizobe, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada

pages 2179-2183


Deactivation of Cd(53 PJ ) by H2 and D2 : Branching Ratios for the Production of CdH and CdD

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Hironobu Umemoto* and Nobuhiro Ohsako

pages 2185-2189


Analysis of the Excitation and Emission Spectra of Tungstates and Molybdate

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Nobuhiro Saito, Noriyuki Sonoyama, and Tadayoshi Sakata*

pages 2191-2194


Towards a Calculation of the Electronic Structures of Macromolecules. I. Quadratically Convergent Method for a Direct Calculation of Localized Molecular Orbitals

GO TO the graphical abstract

Tatsuji Sano and Osamu Matsuoka*,

pages 2195-2199



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Articles
Analitical and Inorganic
=============================

EPR and ENDOR Study of Trigonal Bipyramidal Copper Complexes with a Nitrogen Donor Tripodal Ligand

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Muhammad Q. Ehsan, Yasunori Ohba, Seigo Yamauchi, and Masamoto Iwaizumi*

pages 2201-2209


Charge Distribution Dependent on the Chelating Ratio. [Co( -bpym)(dbbq)2 ] vs. [{Co(dbbq)2 }2 ( -bpym)] (bpym=2,2' -bipyrimidine; dbbq=3,6-di- t -butyl-1,2-benzoquinone)

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Ok-Sang Jung,* Du Hwan Jo, Young-A Lee, Hee Kwon Chae, and Youn Soo Sohn

pages 2211-2214


Aggregation of Phosphoric Acid, Phenyl Dihydrogenphosphate, and Related Organophosphorus Acids in Conductometric Titration with Triethylamine in DMF

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Masashi Hojo,* Hiroshi Hasegawa, and Zhidong Chen

pages 2215-2220


Conformation Control of Model Peptides by Metal Ions. A New Type of Turn Structure Found in [(Boc-Cys-Pro-Leu-Cys-Gly-Ala)Hg]

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Takeshi Yamamura,* Masaya Arai, Tsutomu Yamane, Takeshi Ukai, Masato Ushiyama, and Hiroshi Hirota

pages 2221-2230



=============================
Articles
Orgainc and Biological
=============================

Binding Data Analysis of the Interaction of Bovine Hemoglobin with Dodecyltrimethylammonium Bromide

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Abdul Khalegh Bordbar and Ali Akbar Moosavi-Movahedi*

pages 2231-2234


A Willgerodt-Kindler Type Selenation of Dihalomethane Derivatives, Chloroform, and Sodium Trichloroacetate by Treating with a Base, Elemental Selenium, and an Amine

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Kazuaki Shimada, Minoru Yamaguchi, Tohru Sasaki, Kenji Ohnishi, and Yuji Takikawa*

pages 2235-2242


PM3 Analysis of Nitrone Cycloadditions to Methyl 4,4,4-Trifluoro-2-butenoate

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Kiyoshi Tanaka,* Tatsuya Imase, and Satoru Iwata

pages 2243-2248


Novel Reaction between 3,4,5,6-Tetrachloro-1,2-benzoquinone and Bis-azomethines

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Ashraf A. Aly, Nasr K. Mohamed, Alaa A. Hassan, and Aboul-Fetouh E. Mourad*

pages 2249-2252


Examination of the Conformational Properties of the Prymnesin System : A Computational Chemistry Approach

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Lionel Glendenning, Tomoji Igarashi, and Takeshi Yasumoto*

pages 2253-2263


Asymmetric Transformation of Phenylglyoxal into Mandelic Acid Catalyzed by Cyclodextrin-Based Glyoxalase Models

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Seizo Tamagaki,* Jun Narikawa, and Atsushi Katayama

pages 2265-2268


Enantioselectivity Enhancement of Ester Cleavage by a -Sheet Polypeptide Containing Catalytic Triads in a Serine Protease

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Yasumasa Fukushima

pages 2269-2274


Changes of the Aromatic Character of the Ring in Exocyclically Substituted Derivatives of Benzylic Cation as a Result of Varying Charge at the exo -Carbon Atom

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Tadeusz Marek Krygowski,* Marcin Wisiorowski, Kazuhide Nakata, Mizue Fujio,*, and Yuho Tsuno

pages 2275-2279


Simple Synthesis of trans - , -Dibenzyl- -butyrolactone Lignans by Diastereoselective Reduction of -Benzylidene- -benzyl- -butyrolactones Using NaBH4 -NiCl2

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Yasunori Moritani, Chiaki Fukushima, Toshikazu Miyagishima, Hiroshi Ohmizu,* and Tameo Iwasaki*,

pages 2281-2286


N , N' -Difluoro-1,4-diazoniabicyclo[2.2.2]octane Salts, Highly Reactive and Easy-to-Handle Electrophilic Fluorinating Agents

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Teruo Umemoto* and Masayuki Nagayoshi

pages 2287-2295


Synthesis of Cadinanolide Type of Tricyclic -Methylene- -lactone Using Intramolecular Cyclization of -Trimethylsilylmethyl- , -Unsaturated Ester with Cyclic Ketone

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Chiaki Kuroda* and Kunihito Ito

pages 2297-2303


Interaction of Carbodiimide with Human Erythrocytes: Hemolytic Properties Induced by High Pressure, Heating, and Hypotonic Medium

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Takeo Yamaguchi,* Yoshiya Miyamoto, and Shigeyuki Terada

pages 2305-2308


Dehydrooligopeptides. XIV. Syntheses of 2-[( Z )-1-Amino-1-alken-1-yl]oxazole-4-carboxylic Acid and the Main Common Skeleton of Thiostrepton Peptide Antibiotics, A10255G and J

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Kazuo Okumura, Akio Ito, Hiroyuki Saito, Yutaka Nakamura, and Chung-gi Shin*

pages 2309-2316


Sulfonylation and Phosphinylation of Olefinic Compounds with Radical Species Generated by the Oxidation of Sodium Sulfinates and Diphenylphosphine Oxide

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Takashi Mochizuki, Satoshi Hayakawa, and Koichi Narasaka*

pages 2317-2325


Theoretical Study of the Electronic Structure of 2,2' -Bisilole in Comparison with 1,1' -Bi-1,3-cyclopentadiene: * -* Conjugation and a Low-Lying LUMO as the Origin of the Unusual Optical Properties of 3,3' ,4,4' -Tetraphenyl-2,2' -bisilole

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Shigehiro Yamaguchi and Kohei Tamao*

pages 2327-2334


Preparation of a DNA Complex with Lipoglutamide Having Tetraethylene Glycol Tails, and Its Application to DNA Delivery into Tumor Cells

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Toshinori Sato, Hiroyuki Akino, and Yoshio Okahata*

pages 2335-2340


Palladium(II)-Catalyzed Conjugate Addition of Aromatics to , -Unsaturated Ketones and Aldehydes with Arylantimony Compounds

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Chan Sik Cho, Shin-ichi Motofusa, Kouichi Ohe, and Sakae Uemura*

pages 2341-2348


Reactions of Benzyne with 1,3-Benzodithiole-2-thione and Related Compounds: Formation of Novel Tetracyclic Sulfonium Salts and Their Reactions Leading to Dibenzo-1,3,6,-trithiocin Derivatives

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Juzo Nakayama,* Atsuko Kimata, Hideki Taniguchi, and Fumihiko Takahashi

pages 2349-2354


Radical Dissociation of 2,2' -Bis(2-aryl-3-benzothiophenonyl)s by Mechanical Energy

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Yukie Mori,* Naho Yamada, Miho Kanazawa, Yumiko Horikoshi, Yuka Watanabe, and Koko Maeda

pages 2355-2359


Cation-Exchanged Montmorillonite (Mn+ -Mont)-Catalyzed Prins Reaction

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Jun-ichi Tateiwa, Keiji Hashimoto, Takayoshi Yamauchi, and Sakae Uemura*

pages 2361-2368



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Articles
Applied and Materials
=============================

Comparative Study of the Mutual Separation Characteristics and Mechanism for Neighboring Rare-Earth Elements from Binary Chloride Mixtures and Oxide Mixtures via Vapor Complexes

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Zhi-Chang Wang,* Jin Yu, and Yong-Li Yu

pages 2369-2374


Photomechanical Response of Azobenzene Containing Monolayers on Water Surface

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Takahiro Seki,* Ryo-ichi Fukuda,, Makoto Yokoi,, Takashi Tamaki, and Kunihiro Ichimura

pages 2375-2381


Preparation of Metallic Palladium Catalysts with Thermally Stable Surface Areas and Activities

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Satoru Yada,* Tomoaki Sasaki, Makoto Hiyamizu, and Yuzuru Takagi

pages 2383-2386


Bioactivity of M2 O-TiO2 -SiO2 (M=Na, K) Glasses: An In vitro Evaluation

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Hyun-Min Kim, Fumiaki Miyaji, Tadashi Kokubo,* Masahiko Kobayashi, and Takashi Nakamura

pages 2387-2394


Novel Syntheses of Poly( o -aminobenzoic acid) and Copolymers of o -Aminobenzoic Acid and Aniline as Potential Candidates for Precursor of Polyaniline

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Hu Yan, Hung-Jen Wang, Sanggono Adisasmito, and Naoki Toshima*,

pages 2395-2401



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 69, No. 08 (August, 1996)

RETRUN to the front page

Copyright (C) 1996 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


=============================
Accounts
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2131-2142 (1996) [Vol. 69, No. 8, August, 1996]

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Endohedral Metallofullerenes: New Spherical Cage Molecules with Interesting Properties

Shigeru Nagase,* Kaoru Kobayashi, and Takeshi Akasaka


Illustration

Encapsulation of one or more metals insides hollow fullerene cages is of current interest as new spherical molecules are formed. Recent progress in the production and isolation in macroscopic quantities has made it possible to investigate the interesting properties and reactivities. Theoretical and experimental studies are summarized to show what are known or still unknown for the future material, catalytic, and biological applications.

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=============================
Headline Articles
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2143-2151 (1996) [Vol. 69, No. 8, August, 1996]

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Biological Activity of Water-Soluble Fullerenes. Structural Dependence of DNA Cleavage, Cytotoxicity, and Enzyme Inhibitory Activities Including HIV-Protease Inhibition

Eiichi Nakamura,* Hidetoshi Tokuyama, Shigeru Yamago, Takashi Shiraki, and Yukio Sugiura*,


Illustration

Two classes of water-soluble fullerence derivatives, detergent- and sphere-types, were evaluated for their photo-induced DNA cleaving activity, cytotoxicity against tumor cells, and enzyme inhibitory activity against several proteases including HIV protease.

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=============================
Articles
General and Physical
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2153-2157 (1996) [Vol. 69, No. 8, August, 1996]

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The Study of the Electron-Positron Pair in CS2

Tetsuya Hirade


Illustration

The transition from the bubble state to the mainly non-Ps state takes place between -40 and -110 °C. This phenomena can be explained by the ideas of the ``fourth positron state'' and the ``squeezed Ps state'' proposed by O. E. Mogensen. I measured the effects of varying the surface tension, the dielectric constant, and the temperature. The results of these experiments confirmed these models.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2159-2162 (1996) [Vol. 69, No. 8, August, 1996]

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Electrochemical Reduction of N2 O on Gas-Diffusion Electrodes

Nozomi Konishi, Kohjiro Hara, Akihiko Kudo, and Tadayoshi Sakata*


Illustration

The electrochemical reduction of N2 O to N2 on gas-diffusion electrodes modified by Pt or Ni electrocatalysts at room temperature was studied. The faradaic efficiency of the reduction of N2 O was 100%, even for a low concentration of N2 O gas at a low current density.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2163-2166 (1996) [Vol. 69, No. 8, August, 1996]

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Inclusion Complexation of 4-Biphenylcarboxylate, 4-Biphenylacetate, and 4-Biphenylsulfonate with -Cyclodextrin, Studied by Pulse Radiolysis

Yukio Yamamoto,* Yoichi Yoshida, and Seiichi Tagawa


Illustration

The one-electron reduction of 4-biphenylcarboxylate and 4-biphenylsulfonate by the hydrated electron is effectively retarded by the 1 : 2 complexation with -cyclodextrin ( -CD). No apparent effect of -CD was observed on the one-electron reduction of 4-biphenylacetate, demonstrating that the methylene group sterically inhibits the formation of the 1 : 2 complex.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2167-2171 (1996) [Vol. 69, No. 8, August, 1996]

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Photoinduced Electron Transfer from Cyclic Organogermanium Compounds to C60 Studied by Laser Flash Photolysis

Osamu Ito,* Yoshiko Sasaki, Akira Watanabe, and Kunio Mochida


Illustration

Electron transfer from cyclic germanium compounds to photoexcited C60 in benzonitrile solution has been confirmed by observing the decay of T C60 * and rise of C60 -. transient bands in the near-IR region immediately after 532-nm laser photolysis.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2173-2178 (1996) [Vol. 69, No. 8, August, 1996]

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A Simple New Method for Determining Diffusion Coefficients of Interacting Particles in Porous Silica and Gels

Shigeo Sasaki* and Hiroshi Maeda

The diffusion behavior of NaNO3 from a porous silica sphere into a solution of NaCl was found to be very sensitive to the cross diffusion term when the concentration ratio of NaCl to NaNO3 was high. The diffusion behavior of NaCl, KNO3 , and KI from the inside to the outside of the sphere was also examined. Theoretical equations to analyze the cross diffusion flows of interacting particles were derived. The cross diffusion coefficient of NaNO3 and NaCl as well as the diffusion coefficients of NaNO3 , NaCl, KNO3 , and KI in the porous silica were evaluated from the present experimental results. The obtained diffusion coefficients were found to be about one third of those in solution.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2179-2183 (1996) [Vol. 69, No. 8, August, 1996]

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Hydration and Pressure Effects on the Inter- and Intramolecular Vibrations of Tetramethylpyrazine Crystals

Masayoshi Maehara, Yoshio Suzuki, Hideki Mizobe, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada


Illustration

The hydration and pressure effects on the inter- and intramolecular vibrations of tetramethylpyrazine crystals indicate that the crystals undergo phase transitions under about 1.2 and 2.2 GPa. The hydration causes some changes of electron distribution which strengthen the chemical bonds of the pyrazine ring and weaken the bonds in the methyl group.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2185-2189 (1996) [Vol. 69, No. 8, August, 1996]

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Deactivation of Cd(53 PJ ) by H2 and D2 : Branching Ratios for the Production of CdH and CdD

Hironobu Umemoto* and Nobuhiro Ohsako


Illustration

The branching ratios for the production of CdH(CdD) in the reactions of Cd(53P1 ) and Cd(53P0 ) with H2 (D2 ) were determined by using a laser excitation-depletion technique. The ratios were J independent, and were determined to be 0.81 ± 0.04 for H2 and 0.76 ± 0.06 for D2 .

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2191-2194 (1996) [Vol. 69, No. 8, August, 1996]

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Analysis of the Excitation and Emission Spectra of Tungstates and Molybdate

Nobuhiro Saito, Noriyuki Sonoyama, and Tadayoshi Sakata*


Illustration

The excitation and emission spectra of the tungstates and molybdate were analyzed by a configurational coordination model. E0 , the energy level of the excited triplet state and reorganization energies at the ground state and the triplet state were determined for these salts.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2195-2199 (1996) [Vol. 69, No. 8, August, 1996]

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Towards a Calculation of the Electronic Structures of Macromolecules. I. Quadratically Convergent Method for a Direct Calculation of Localized Molecular Orbitals

Tatsuji Sano and Osamu Matsuoka*,

A super configuration-interaction method has been formulated and tested for the direct calculation of orthogonal localized molecular orbitals. This method has been designed for the calculation of the electronic structures of macromolecules; also, its iterative procedure has been proven to converge quadratically, while retaining the initial forms of the localized orbitals.

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=============================
Articles
Analitical and Inorganic
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2201-2209 (1996) [Vol. 69, No. 8, August, 1996]

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EPR and ENDOR Study of Trigonal Bipyramidal Copper Complexes with a Nitrogen Donor Tripodal Ligand

Muhammad Q. Ehsan, Yasunori Ohba, Seigo Yamauchi, and Masamoto Iwaizumi*


Illustration

The hyperfine couplings and nuclear quadrupole interactions of the coordinating nitrogens of the title complexes were determined by powder ENDOR. Based on these data and EPR analysis, the pliability to rhombic distortion, the ligand field effects on the spin distribution and other features of the electronic structure of trigonal bipyramidal copper complexes were clarified.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2211-2214 (1996) [Vol. 69, No. 8, August, 1996]

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Charge Distribution Dependent on the Chelating Ratio. [Co( -bpym)(dbbq)2 ] vs. [{Co(dbbq)2 }2 ( -bpym)] (bpym=2,2' -bipyrimidine; dbbq=3,6-di- t -butyl-1,2-benzoquinone)

Ok-Sang Jung,* Du Hwan Jo, Young-A Lee, Hee Kwon Chae, and Youn Soo Sohn


Illustration

The mononuclear complex [Co( -bpym)(dbbq)2 ] exists as a mixture of Co(III) and Co(II) redox isomers dependent on the temperature in the solid state. In striking contrast, the binuclear complex [{Co(dbbq)2 }2 ( -bpym)] is locked in a charge distribution of [{CoII (dbsq)2 }2 ( -bpym)] when the temperature is 100-400 K.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2215-2220 (1996) [Vol. 69, No. 8, August, 1996]

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Aggregation of Phosphoric Acid, Phenyl Dihydrogenphosphate, and Related Organophosphorus Acids in Conductometric Titration with Triethylamine in DMF

Masashi Hojo,* Hiroshi Hasegawa, and Zhidong Chen


Illustration

In conductometric titrations with Et3 N in DMF, although phosphoric acid or phenyl dihydrogenphosphate (PhOPO(OH)2 ) gave a maximum at the half-equivalence point, diphenyl hydrogenphosphate ((PhO)2 PO(OH)) did not. The appearance of the maximum was explained by homoconjugation between an acid (HA) and the conjugate anion (A- ) upon neutralization with the base (B) in DMF: B+2HABH+...HA2- .

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2221-2230 (1996) [Vol. 69, No. 8, August, 1996]

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Conformation Control of Model Peptides by Metal Ions. A New Type of Turn Structure Found in [(Boc-Cys-Pro-Leu-Cys-Gly-Ala)Hg]

Takeshi Yamamura,* Masaya Arai, Tsutomu Yamane, Takeshi Ukai, Masato Ushiyama, and Hiroshi Hirota


Illustration

The structure of [(Boc-Cys1 -Pro-Leu-Cys4 -Gly-Ala-OMe)Hg], 1 , in solution was studied by XAFS, NMR, RMD, and molecular dynamics. The linear coordinate mercury (Hg2+ ) controls the peptide conformation so as to take a new type of turn structure.

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=============================
Articles
Orgainc and Biological
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2231-2234 (1996) [Vol. 69, No. 8, August, 1996]

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Binding Data Analysis of the Interaction of Bovine Hemoglobin with Dodecyltrimethylammonium Bromide

Abdul Khalegh Bordbar and Ali Akbar Moosavi-Movahedi*

The thermodynamic parameters for binding of dodecyltrimethylammonium bromide with bovine hemoglobin have been investigated by using the Wyman binding potential and median ligand activity concepts. The unusual shape of the Scatchard plot at 300 K was interpreted by considering the electrostatic and hydrophobic binding sets and the free energy of binding has been resolved to electrostatic and hydrophobic free energies of interaction, G=Gelec, + Ghyd, . At 80 predominant unfolding occurres and Gelec, is equal to -24 and Ghyd, is equal to -5 kJ mol-1 .

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2235-2242 (1996) [Vol. 69, No. 8, August, 1996]

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A Willgerodt-Kindler Type Selenation of Dihalomethane Derivatives, Chloroform, and Sodium Trichloroacetate by Treating with a Base, Elemental Selenium, and an Amine

Kazuaki Shimada, Minoru Yamaguchi, Tohru Sasaki, Kenji Ohnishi, and Yuji Takikawa*


Illustration

The treatment of dihalomethane derivatives, chloroform, or sodium trichloroacetate with elemental selenium in the presence of NaH and an amine at 80-130 °C or under ultrasonic irradiation at room temperature gave the corresponding selenoamides or seleoureas in modest yields.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2243-2248 (1996) [Vol. 69, No. 8, August, 1996]

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PM3 Analysis of Nitrone Cycloadditions to Methyl 4,4,4-Trifluoro-2-butenoate

Kiyoshi Tanaka,* Tatsuya Imase, and Satoru Iwata


Illustration

3,4-Dihydroisoquinoline N -oxide cycloadded with trifluoro-2-butenoate to give a mixture of 1,10b-cis - and -trans -cycloadducts in a ratio of 3 : 1, and with 2-butenoate to afford the 1,10b-cis -cycloadduct exclusively. The stereoselectivity in the cycloadditions was reproduced by calculations of the transition structures by the PM3 method.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2249-2252 (1996) [Vol. 69, No. 8, August, 1996]

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Novel Reaction between 3,4,5,6-Tetrachloro-1,2-benzoquinone and Bis-azomethines

Ashraf A. Aly, Nasr K. Mohamed, Alaa A. Hassan, and Aboul-Fetouh E. Mourad*


Illustration

3,4,5,6-Tetrachloro-1,2-benzoquinone (CHL-o ) reacted with N ,N' -dicyclohexyl-1,2-ethane-, and p -xylenediimine to give a transient condensation product, which underwent a [4+2 ] cycloaddition reaction. N ,N' -Diaryl-1,2-ethane- and p -xylenediimines and led to production of substituted CHL-o , followed by a [4+2 ] cycloaddition reaction.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2253-2263 (1996) [Vol. 69, No. 8, August, 1996]

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Examination of the Conformational Properties of the Prymnesin System : A Computational Chemistry Approach

Lionel Glendenning, Tomoji Igarashi, and Takeshi Yasumoto*


Illustration

A variety of contemporary conformational searching techniques and three widely available and consistently used hydrocarbon force fields were used to probe the three-dimensional space of the conformationally-rich and functionally diverse potent ichthyotoxins collectively named ``prymnesins''.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2265-2268 (1996) [Vol. 69, No. 8, August, 1996]

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Asymmetric Transformation of Phenylglyoxal into Mandelic Acid Catalyzed by Cyclodextrin-Based Glyoxalase Models

Seizo Tamagaki,* Jun Narikawa, and Atsushi Katayama


Illustration

(2-Mercaptoethyl)amino-attached cyclodextrin provides a highly enantioselective environment during the transformation of phenylglyoxal into (S )-mandelic acid, although simple inclusion into native -, -, and -cyclodextrins and 2-hydroxypropyl and methyl variants is not sufficient to cause appreciable asymmetric induction.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2269-2274 (1996) [Vol. 69, No. 8, August, 1996]

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Enantioselectivity Enhancement of Ester Cleavage by a -Sheet Polypeptide Containing Catalytic Triads in a Serine Protease

Yasumasa Fukushima


Illustration

Poly(Asp-Leu-His-Leu-Ser-Leu) with a -sheet structure has more effective catalytic activity and higher enantioselectivity than the peptide hexamer. The hydrolytic properties were affected by the secondary structural content of the polypeptide.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2275-2279 (1996) [Vol. 69, No. 8, August, 1996]

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Changes of the Aromatic Character of the Ring in Exocyclically Substituted Derivatives of Benzylic Cation as a Result of Varying Charge at the exo -Carbon Atom

Tadeusz Marek Krygowski,* Marcin Wisiorowski, Kazuhide Nakata, Mizue Fujio,*, and Yuho Tsuno


Illustration

Steric hindrance of the exocyclic substituents R1 and R2 cause variations in charge distribution in the cation, leading to considerable changes in geometry of the ring and in consequence in its aromatic character. The changes in aromaticity are mostly due to geometric terms, i.e. alternation of the bond lengths.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2281-2286 (1996) [Vol. 69, No. 8, August, 1996]

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Simple Synthesis of trans - , -Dibenzyl- -butyrolactone Lignans by Diastereoselective Reduction of -Benzylidene- -benzyl- -butyrolactones Using NaBH4 -NiCl2

Yasunori Moritani, Chiaki Fukushima, Toshikazu Miyagishima, Hiroshi Ohmizu,* and Tameo Iwasaki*,


Illustration

trans - , -Dibenzyl- -butyrolactones ( 1 ) were synthesized by stereoselective reduction of -benzylidenelactones ( 3 ). The reduction is found to proceed via conjugate addition of hydride and stereoselective protonation of the resulting enolate ( 2 ). The stereoselectivity would be brought about by conformational rigidity of the phenyl moiety of the -benzyl group induced by 1,3-allylic strain.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2287-2295 (1996) [Vol. 69, No. 8, August, 1996]

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N , N' -Difluoro-1,4-diazoniabicyclo[2.2.2]octane Salts, Highly Reactive and Easy-to-Handle Electrophilic Fluorinating Agents

Teruo Umemoto* and Masayuki Nagayoshi


Illustration

The titled salts 1 were synthesized in pure form by the direct fluorination of 1,4-diazabicyclo[2.2.2]octane in the presence of a Brnsted acid, or fluorination followed by a counteranion replacement reaction, and were demonstrated to serve as widely applicable fluorinating agents.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2297-2303 (1996) [Vol. 69, No. 8, August, 1996]

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Synthesis of Cadinanolide Type of Tricyclic -Methylene- -lactone Using Intramolecular Cyclization of -Trimethylsilylmethyl- , -Unsaturated Ester with Cyclic Ketone

Chiaki Kuroda* and Kunihito Ito


Illustration

-Methylene- -lactones fused to a perhydronaphthalene carbon framework, model compounds of cadinanolides, were synthesized by fluoride-promoted intramolecular cyclization of -(ethoxycarbonyl)allylsilane with cyclic ketone followed by lactonization. It was found that both Lewis acid- and fluoride-promoted cyclizations gave a trans -decaline system mainly.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2305-2308 (1996) [Vol. 69, No. 8, August, 1996]

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Interaction of Carbodiimide with Human Erythrocytes: Hemolytic Properties Induced by High Pressure, Heating, and Hypotonic Medium

Takeo Yamaguchi,* Yoshiya Miyamoto, and Shigeyuki Terada


Illustration

The effects of carbodiimide on hemolysis of human erythrocytes were examined. On the basis of data concerning the ion transport and cross-linking of membrane proteins, we have found that high-pressure-, or heat-induced hemolysis, compared with osmotic hemolysis, is suppressed by a stabilization of the cytoskeletal network.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2309-2316 (1996) [Vol. 69, No. 8, August, 1996]

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Dehydrooligopeptides. XIV. Syntheses of 2-[( Z )-1-Amino-1-alken-1-yl]oxazole-4-carboxylic Acid and the Main Common Skeleton of Thiostrepton Peptide Antibiotics, A10255G and J

Kazuo Okumura, Akio Ito, Hiroyuki Saito, Yutaka Nakamura, and Chung-gi Shin*


Illustration

The general synthesis of methyl 2-[(Z )-1-amino-1-alkenyl]oxazole-4-carboxylates was accomplished. Furthermore, the practical synthesis of the common main dehydropentapeptide constituting thiostrepton macrocyclic peptide antibiotics, A10255G and J, was first done.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2317-2325 (1996) [Vol. 69, No. 8, August, 1996]

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Sulfonylation and Phosphinylation of Olefinic Compounds with Radical Species Generated by the Oxidation of Sodium Sulfinates and Diphenylphosphine Oxide

Takashi Mochizuki, Satoshi Hayakawa, and Koichi Narasaka*


Illustration

Sodium arenesulfinates are oxidized with manganese(III) 2-pyridinecarboxylate or ammonium cerium(IV) nitrates to generate sulfonyl radicals, which add to olefinic compounds to afford sulfonylated products in good yield. Diphenylphosphinyl radical is also generated by treating diphenylphosphine oxide with manganese(III) 2-pyridinecarboxylate and reacts with olefinic compounds, giving phosphinylated products.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2327-2334 (1996) [Vol. 69, No. 8, August, 1996]

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Theoretical Study of the Electronic Structure of 2,2' -Bisilole in Comparison with 1,1' -Bi-1,3-cyclopentadiene: * -* Conjugation and a Low-Lying LUMO as the Origin of the Unusual Optical Properties of 3,3' ,4,4' -Tetraphenyl-2,2' -bisilole

Shigehiro Yamaguchi and Kohei Tamao*

Theoretical calculations on the electronic structure of a parent 2,2' -bisilole in comparison with its carbon analog, 1,1' -bi-1,3-cyclopentadiene, reveals that the origin of the unusually long UV-vis absorption maximum of 3,3' ,4,4' -tetraphenyl-2,2' -bisilole is ascribed to a low-lying LUMO arising from the * -* conjugation enhanced by structural distortions.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2335-2340 (1996) [Vol. 69, No. 8, August, 1996]

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Preparation of a DNA Complex with Lipoglutamide Having Tetraethylene Glycol Tails, and Its Application to DNA Delivery into Tumor Cells

Toshinori Sato, Hiroyuki Akino, and Yoshio Okahata*


Illustration

We newly prepared a polyion complex of DNA with lipoglutamide 2EO4 C6 N+ . The DNA/2EO4 C6 N+ complex showed high solubility in water, low cytotoxicity, and uptake efficiency into tumor cells, compared with the DNA complex without tetraethyleneglycol.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2341-2348 (1996) [Vol. 69, No. 8, August, 1996]

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Palladium(II)-Catalyzed Conjugate Addition of Aromatics to , -Unsaturated Ketones and Aldehydes with Arylantimony Compounds

Chan Sik Cho, Shin-ichi Motofusa, Kouichi Ohe, and Sakae Uemura*


Illustration

Triarylstibines react with , -unsaturated ketones and aldehydes in acetic acid in the presence of Pd(OAc)2 (catalytic) and AgOAc to afford the conjugate addition products in good yields, while diarylantimony chlorides, arylantimony dichlorides and diphenylantimony acetate react similarly, even in the absence of AgOAc, to afford the same products in higher yields.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2349-2354 (1996) [Vol. 69, No. 8, August, 1996]

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Reactions of Benzyne with 1,3-Benzodithiole-2-thione and Related Compounds: Formation of Novel Tetracyclic Sulfonium Salts and Their Reactions Leading to Dibenzo-1,3,6,-trithiocin Derivatives

Juzo Nakayama,* Atsuko Kimata, Hideki Taniguchi, and Fumihiko Takahashi


Illustration

The reaction of 1,3-benzodithiole-2-thione with 2-carboxybenzenediazonium chloride gives the sulfonium salt 7 , which is converted to trithiocin derivatives, such as 22 .

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2355-2359 (1996) [Vol. 69, No. 8, August, 1996]

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Radical Dissociation of 2,2' -Bis(2-aryl-3-benzothiophenonyl)s by Mechanical Energy

Yukie Mori,* Naho Yamada, Miho Kanazawa, Yumiko Horikoshi, Yuka Watanabe, and Koko Maeda


Illustration

The title compounds underwent homolytic cleavage of the central C-C bond on applying pressure in the solid state. The reactivity depended on the substituents on the phenyl ring and the presence of solvent of crystallization.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2361-2368 (1996) [Vol. 69, No. 8, August, 1996]

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Cation-Exchanged Montmorillonite (Mn+ -Mont)-Catalyzed Prins Reaction

Jun-ichi Tateiwa, Keiji Hashimoto, Takayoshi Yamauchi, and Sakae Uemura*


Illustration

A Prins reaction of styrenes with paraformaldehyde or 1,3,5-trioxane in toluene in the presence of cation-exchanged montmorillonite (Mn+ -mont) at 80 °C produced 4-aryl-1,3-dioxanes selectively in up to 99% isolated yield with a turnover number of up to 5.9×102 .

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Articles
Applied and Materials
=============================


Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2369-2374 (1996) [Vol. 69, No. 8, August, 1996]

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Comparative Study of the Mutual Separation Characteristics and Mechanism for Neighboring Rare-Earth Elements from Binary Chloride Mixtures and Oxide Mixtures via Vapor Complexes

Zhi-Chang Wang,* Jin Yu, and Yong-Li Yu


Illustration

A comparative study of the mutual separation characteristics was made for the neighboring rare-earth elements La, Ce, Pr, and Nd from their binary chloride mixtures and oxide mixtures using a chemical vapor-transport reaction. Separation factors of up to (A) 21.4 for La : Ce, (B) ⩾ 100 for Pr : Ce, and (C) 1.84 for Pr : Nd were observed from their oxide mixtures, which were larger than from their chloride mixtures.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2375-2381 (1996) [Vol. 69, No. 8, August, 1996]

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Photomechanical Response of Azobenzene Containing Monolayers on Water Surface

Takahiro Seki,* Ryo-ichi Fukuda,, Makoto Yokoi,, Takashi Tamaki, and Kunihiro Ichimura


Illustration

Monolayers of an amphiphilic polymer and related low-molecular-mass compounds containing an azobenzene unit were spread on a water surface, and the photoinduced deformation of these films were investigated. Important roles of the hydrophilic head group on the azobenzene packing state and the photomechanical behavior were indicated.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2383-2386 (1996) [Vol. 69, No. 8, August, 1996]

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Preparation of Metallic Palladium Catalysts with Thermally Stable Surface Areas and Activities

Satoru Yada,* Tomoaki Sasaki, Makoto Hiyamizu, and Yuzuru Takagi


Illustration

Pd metal catalysts were prepared by the reaction of palladium(II) chloride with sodium aluminate (Type A) or with sodium hydroxide (Type N). The type A catalysts treated at high reduction temperature did not lose activities in the hydrogenation of nitrobenzene, compared to the catalyst treated at 25 °C. The activities of the type N catalysts decreased with increased reduction temperature.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2387-2394 (1996) [Vol. 69, No. 8, August, 1996]

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Bioactivity of M2 O-TiO2 -SiO2 (M=Na, K) Glasses: An In vitro Evaluation

Hyun-Min Kim, Fumiaki Miyaji, Tadashi Kokubo,* Masahiko Kobayashi, and Takashi Nakamura


Illustration

Alkali titanate-based glasses form a bonelike apatite layer in simulated body fluid with ion concentrations nearly equal to those of human blood plasma, as shown in the following illustration. This indicates that alkali titanates as well as alkali silicates can be basic components of bioactive materials.

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Copyright (C) 1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 69, 2395-2401 (1996) [Vol. 69, No. 8, August, 1996]

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Novel Syntheses of Poly( o -aminobenzoic acid) and Copolymers of o -Aminobenzoic Acid and Aniline as Potential Candidates for Precursor of Polyaniline

Hu Yan, Hung-Jen Wang, Sanggono Adisasmito, and Naoki Toshima*,


Illustration

Poly(o -aminobenzoic acid) and copolymers of o -aminobenzoic acid and aniline were synthesized as excellent candidates for the precursor of polyaniline by heat treatment. The reaction yield can be dramatically improved by addition of sodium hydroxide.

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