Bulletin of the Chemical Society of Japan

Vol. 68, No. 07 (July, 1995)

RETRUN to the front page

Copyright (C) 1995 by The Chemical Society of Japan


CONTENTS


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

Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2' -Bi-1 H -imidazole System. I. Acid Dissociation Constants and Redox Properties in Solution

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Tomoyuki Akutagawa*, and Gunzi Saito

pages 1753-1773


Structure of Clusters in Ethanol-Water Binary Solutions Studied by Mass Spectrometry and X-Ray Diffraction

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Masaki Matsumoto, Nobuyuki Nishi,* Toshiya Furusawa, Masaru Saita, Toshiyuki Takamuku, Motoyuki Yamagami, and Toshio Yamaguchi,

pages 1775-1783


Characterization of Enantiomeric Pairs of Optically Active 10-P-5 Phosphoranes with Asymmetry Only at Phosphorus

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Satoshi Kojima, Kazumasa Kajiyama, and Kin-ya Akiba*

pages 1785-1797


Halofluorination of Alkenes Using Dilute Hydrofluoric Acid

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Manabu Kuroboshi* and Tamejiro Hiyama

pages 1799-1805



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

The Quenching of Lumichrome Fluorescence by -Cyclodextrin : Evidence for Inclusion Complex

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Biswajit Sarkar, Utpal Das, Subirnath Bhattacharyya, and Swapan K. Bose*

pages 1807-1809


Semiconductor Photocatalysis.1) ZnS-Nanocrystallite-Catalyzed Photooxidation of Organic Compounds

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Shozo Yanagida,* Hiroshi Kawakami, Yoshihide Midori, Hirotoshi Kizumoto, Chongjin Pac, and Yuji Wada

pages 1811-1823


Spectroscopic and Conductometric Studies of Lanthanide Soaps

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Krishna N. Mehrotra, Rajeev K. Shukla, and Mithlesh Chauhan*

pages 1825-1831


Effect of Counterions on the Surface Adsorption and Volume Behavior of Micelle-Forming Local Anesthetics

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Hitoshi Matsuki,* Michio Yamanaka, and Shoji Kaneshina

pages 1833-1838


Kinetics of Oxygen Exchange between Arsenic Acid and Solvent Water

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Akiko Okumura,* Yuko Matsumiya, Kasumi Yamamoto, Reiko Ueno, Mariko Suzuki, and Shinichi Yamabe

pages 1839-1849


Effect of Sonolysis on Acid Degradation of Chitin to Form Oligosaccharides

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Yasuko Takahashi,* Fumie Miki, and Kazuko Nagase

pages 1851-1857


Direct Determination of the Intermolecular Pair-Potential Energy Function of Methane from the Extended Principal of the Corresponding States

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Elaheh K. Goharshadi* and Ali Boushehri

pages 1859-1861


Molecular Reorientation in AlBr3 .NH3 , as Studied by the 81 Br Nuclear Quadrupole Resonance

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Hideta Ishihara,* Koji Yamada, Tsutomu Okuda, and Alarich Weiss

pages 1863-1866


N , N -Dimethylformamide+2-Methoxyethanol Binary Mixtures. Viscosity and Activation Energy of Viscous Flow at Various Temperatures

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Fulvio Corradini, GianCarlo Franchini, Andrea Marchetti, Mara Tagliazucchi, and Lorenzo Tassi*

pages 1867-1872


Formation of the Oxanickelacyclopentene Complex from Nickel(0), Carbon Dioxide, and Alkyne. An ab initio MO/SD-CI Study. Part II. Reactivity and Regioselectivity of Hydroxyacetylene

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Shigeyoshi Sakaki,* Kazuya Mine, Taisuke Hamada, and Toru Arai

pages 1873-1882


Pressure-Induced Phase Transition in the 1,2,4,5-Tetrabromobenzene Crystal

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Fumio Shimizu, Yoshio Suzuki, Keiko Mitarai, Mitsuyo Fujino, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada

pages 1883-1888


Kinetics of Electrochemical Reduction of Carbon Dioxide on a Gold Electrode in Phosphate Buffer Solutions

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Hidetomo Noda, Shoichiro Ikeda,* Akio Yamamoto, Hisahiko Einaga, and Kaname Ito

pages 1889-1895


Ultraviolet Photoelectron Spectroscopy of Alkaline-Metal Doped Polyacetylene

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Takayuki Miyamae,*, Koji Kamiya, Shinji Hasegawa, Kazuhiko Seki, Chizuko Tanaka, and Jiro Tanaka

pages 1897-1903


IR Investigation of Selective Reduction of NO by Ethene on Cu-ZSM-5

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Takeshi Tabata,* Hirofumi Ohtsuka, Mikako Kokitsu, and Osamu Okada

pages 1905-1914


Segmented Contractions of Gaussian Basis Sets for Relativistic Molecular Calculations

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Yoshihiro Watanabe and Osamu Matsuoka*

pages 1915-1919



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

Micro Enzyme-Sensor with an Osmium Complex and Porous Carbon for Measuring Galactose

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Kazuhisa Miyata,* Masahiko Fujiwara, Junko Motonaka, Toshihiro Moriga, and Ichiro Nakabayashi

pages 1921-1927


Synergistic Extraction of Rare Earths(III) with -Diketone and Nitrogen-Containing Terdentate Ligand, 2,2' :6' ,2'' -Terpyridine

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Saeko Satake, Satoshi Tsukahara,* and Nobuo Suzuki

pages 1929-1933


Mssbauer Emission Spectra of 119 Sn in Binary Compounds of Antimony and Tellurium

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Shizuko Ambe* and Fumitoshi Ambe

pages 1935-1940


Kinetics and Mechanism of the High-Temperature Selenidization of Titanium

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Haruo Naruke,* Kenji Yamada, Kazuyuki Kakegawa, and Yoshinori Sasaki

pages 1941-1945


Kinetics and Mechanisms of Photoinduced Reduction of Methylviologen by N -Alkyltetraphenylporphyrinatozinc(II) in Methanol

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Keiichi Tsukahara,* Naoko Sawai, Satoko Hamada, Takashi Nakazawa, and Ryoichi Nakagaki

pages 1947-1954


Kinetic Study of Interconversion between Two Geometrical Isomers of the Methoxy-Bridged Bis(silylene)iron Complex, ( -C5 Me5 )(OC)Fe{(SiMe2 )...OMe...(SiMeOMe)}

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Keiji Ueno* and Hiroshi Ogino*

pages 1955-1958



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

Synthesis and Characterization of Hybrid Porphyrin Dimers and Halogenated Porphyrin Dimers

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Kouji Iida, Mamoru Nango,* Kenichi Okada, Masaya Hikita, Mitsutaka Matsuura, Takayuki Kurihara, Takeharu Tajima, Ayako Hattori, Shinichi Ishikawa, Keiji Yamashita, Kazuichi Tsuda,* and Yukihisa Kurono

pages 1959-1968


A Novel Dehydrative Ring-Transformation of 1-Alkyl-3-aroylpyrrolidines into 1-Alkyl-2-aryl-3-methylpyrroles

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Shuntaro Mataka,* Hirohisa Kitagawa, Takehito Tsukinoki, Masashi Tashiro, Kazufumi Takahashi, and Kichinosuke Kamata

pages 1969-1979


Novel C5-Substituted 2' -Deoxyuridine Derivatives Bearing Amino-Linker Arms: Synthesis, Incorporation into Oligodeoxyribonucleotides, and Their Hybridization Properties

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Hiroaki Ozaki, Akiko Nakamura, Midori Arai, Masakazu Endo, and Hiroaki Sawai*

pages 1981-1987


A Membrane Protein Model: Polypeptides with Four -Helix Bundle Structure on 5,10,15,20-Tetrakis[2-(carboxymethoxy)phenyl]porphyrin

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Toru Arai, Keisuke Kobata, Hisakazu Mihara, Tsutomu Fujimoto, and Norikazu Nishino*

pages 1989-1998


Manganese(III)-Mediated Oxidative Radical Cyclization 2. Reaction of 1,1, , -Tetraarylsubstituted Terminal Alkadienes with Malonamide or Acetoacetamide

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Hiroshi Nishino,* Hideaki Hashimoto, James D. Korp, and Kazu Kurosawa

pages 1999-2009


Synthesis and Dynamic Stereochemistry of a Tri(1-azulenyl)methyl Cation Containing a Different Substituent on Each Azulene Ring

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Shunji Ito, Noboru Morita, and Toyonobu Asao*

pages 2011-2016


A Novel Enzymatic Decarboxylation Proceeds via a Thiol Ester Intermediate

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Takayasu Kawasaki, Masakatsu Watanabe, and Hiromichi Ohta*

pages 2017-2020


Effect of a Liquid-Liquid Phase Separation on the Slopes of Density vs. Concentration Plots

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Isamu Inamura,* Yuji Jinbo, Yoriko Akiyama, and Yasuo Kubo

pages 2021-2023


Preparation and Chemical Reactions of Trifluoroacetaldehyde Azine (1,1,1,6,6,6-Hexafluoro-3,4-diaza-2,4-hexadiene)

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Akihito Hashidzume, Atsushi Kajiwara, Akira Harada, Mikiharu Kamachi,* and Masami Kusunoki

pages 2025-2031


Studies of the Selective O -Alkylation and Dealkylation of Flavonoids. XVIII. A Convenient Method for Synthesizing 3,5,6,7-Tetrahydroxyflavones

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Tokunaru Horie,* Takashi Kobayashi, Yasuhiko Kawamura, Isao Yoshida, Hideaki Tominaga, and Kazuyo Yamashita

pages 2033-2041


Direct CC Triple Bond Formation from the C=C Double Bond and Direct Hydroxylation into the o -Position of a Nitro Group on the Benzene Nucleus with Potassium t -Butoxide in N , N -Dimethylformamide in the Air

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Shuzo Akiyama,* Kunihiko Tajima, Shin'ichi Nakatsuji, Kenichiro Nakashima, Kazuko Abiru, and Miwa Watanabe

pages 2043-2051


Hafnium(IV) Trifluoromethanesulfonate, An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reactions

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Iwao Hachiya, Mitsuhiro Moriwaki, and Sh Kobayashi*

pages 2053-2060



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

Studies on the Complex Formation between Iron(III) or Copper(II) and Poly(vinyl alcohol) in Terms of Inclusion of the Metal Hydroxide-Like Clusters by the Polymer

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Hiroshi Yokoi,* Yasuyoshi Mori, and Yutaka Fujise

pages 2061-2065


Study on the Interaction between Iron(III) Hydroxide Oxide and Cation Exchange Resins

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Ichiro Inami* and Takao Baba

pages 2067-2072


Formalized Drawing of Fullerene Nets. 1. Algorithm and Exhaustive Generation of Isomeric Structures

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Mitsuho Yoshida and Eiji sawa*

pages 2073-2081


Formalized Drawing of Fullerene Nets. 2. Applications to Mapping of Pyracylene Rearrangements, C2 -Insertion/Elimination Pathways, and Leapfrog/Carbon Cylinder Operations

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Mitsuho Yoshida and Eiji sawa*

pages 2083-2092



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 68, No. 07 (July, 1995)

RETRUN to the front page

Copyright (C) 1995 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1753-1773 (1995) [Vol. 68, No. 7, July, 1995]

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Multiplex Proton-Transfer and Electron-Transfer Natures Based on the 2,2' -Bi-1 H -imidazole System. I. Acid Dissociation Constants and Redox Properties in Solution

Tomoyuki Akutagawa*, and Gunzi Saito


Illustration

2,2' -Bi-1H -imidazole ( 1 ) derivatives construct a new proton-transfer and electron-transfer system. The measurements of acid dissociation constants and redox potentials in solution indicated high acidity and stabilization of cation species 2 and 3 . The on-site Coulomb repulsion energy was estimated for various types of electron and/or proton acceptors and donors.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1775-1783 (1995) [Vol. 68, No. 7, July, 1995]

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Structure of Clusters in Ethanol-Water Binary Solutions Studied by Mass Spectrometry and X-Ray Diffraction

Masaki Matsumoto, Nobuyuki Nishi,* Toshiya Furusawa, Masaru Saita, Toshiyuki Takamuku, Motoyuki Yamagami, and Toshio Yamaguchi,


Illustration

The structure of clusters in ethanol-water binary solutions with xE0.2 was investigated by a mass-spectrometric analysis of clusters isolated from liquid droplets and X-ray diffraction measurements of an intact solution. The most likely model of the binary clusters is presented based on a mass-spectral analysis and the concentration dependence of the radial distribution functions.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1785-1797 (1995) [Vol. 68, No. 7, July, 1995]

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Characterization of Enantiomeric Pairs of Optically Active 10-P-5 Phosphoranes with Asymmetry Only at Phosphorus

Satoshi Kojima, Kazumasa Kajiyama, and Kin-ya Akiba*


Illustration

The first enantiomeric pairs of optically active 10-P-5 phosphoranes of definable stereochemistry with asymmetry only at phosphorus, 4 - RP and 4 - SP (R=CH2CH2OH ), and 2 - RP and 2 - SP (R=H ), could be obtained respectively by chemical transformation of easily separable diastereomers 3 - RP and 3 - SP (R=CH2CO2 -(-)-menthyl), and 10 - RP and 10 - SP (R=CH2NHC*HCH3Ph ).

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1799-1805 (1995) [Vol. 68, No. 7, July, 1995]

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Halofluorination of Alkenes Using Dilute Hydrofluoric Acid

Manabu Kuroboshi* and Tamejiro Hiyama


Illustration

Dilute (1 M) hydrofluoric acid was found to be applicable to iodofluorination of alkenes using together with N -iodosuccinimide, KHF2 , and a phase-transfer catalyst (n -Bu)4 NF. H2 F3- was shown to be the active fluorinating species.

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1807-1809 (1995) [Vol. 68, No. 7, July, 1995]

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The Quenching of Lumichrome Fluorescence by -Cyclodextrin : Evidence for Inclusion Complex

Biswajit Sarkar, Utpal Das, Subirnath Bhattacharyya, and Swapan K. Bose*


Illustration

Lumichrome forms 1 : 1 inclusion complex with -cyclodextrin in aqueous solution. Solubility and fluorescence quenching of lumichrome in the presence of -cyclodextrin have been studied. The values of equilibrium constant (K ) obtained from two different methods are in good agreement.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1811-1823 (1995) [Vol. 68, No. 7, July, 1995]

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Semiconductor Photocatalysis.1) ZnS-Nanocrystallite-Catalyzed Photooxidation of Organic Compounds

Shozo Yanagida,* Hiroshi Kawakami, Yoshihide Midori, Hirotoshi Kizumoto, Chongjin Pac, and Yuji Wada


Illustration

While the photoformed electron on ZnS nanocrystallites reduces water to H2 , the concomitantly photoformed hole oxidizes aliphatic amines, alcohols, and some alkylated aromatic compounds, leading to the coupling reactions of the intermediary -radicals. The formation and stabilization of the -radicals in the photocatalysis is discussed in view of MO calculations.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1825-1831 (1995) [Vol. 68, No. 7, July, 1995]

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Spectroscopic and Conductometric Studies of Lanthanide Soaps

Krishna N. Mehrotra, Rajeev K. Shukla, and Mithlesh Chauhan*

IR studies of cerium, didymium, neodymium, and samarium soaps revealed the ionic nature of the metal oxygen bond in these soaps. The double-layer structure of soaps was confirmed by X-ray diffraction analysis. The micellar behavior and nature of soap solutions in a benzene-DMF mixture (50% v/v) were investigated by conductometric investigations.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1833-1838 (1995) [Vol. 68, No. 7, July, 1995]

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Effect of Counterions on the Surface Adsorption and Volume Behavior of Micelle-Forming Local Anesthetics

Hitoshi Matsuki,* Michio Yamanaka, and Shoji Kaneshina


Illustration

Micelle-forming local anesthetic dibucaine and tetracaine with various halide counterions were found to undergo a phase transition from a gaseous state to an expanded state at low concentrations. The effect of counterions on their surface adsorption and volume behavior is discussed on the basis of the evaluated thermodynamic quantities.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1839-1849 (1995) [Vol. 68, No. 7, July, 1995]

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Kinetics of Oxygen Exchange between Arsenic Acid and Solvent Water

Akiko Okumura,* Yuko Matsumiya, Kasumi Yamamoto, Reiko Ueno, Mariko Suzuki, and Shinichi Yamabe


Illustration

The exchange rates were measured over the (0-12) pH range using 18 O tracer and 17 O NMR methods. Various ionic species (H3 AsO4 , H2 AsO4 - , HAsO4 2- , and AsO4 3- ) exchange their oxygens with water via the following paths: (a) unimolecular and (b) bimolecular (reversible condensation reactions between these species). The rate constants and the activation parameters for elementary processes were evaluated.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1851-1857 (1995) [Vol. 68, No. 7, July, 1995]

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Effect of Sonolysis on Acid Degradation of Chitin to Form Oligosaccharides

Yasuko Takahashi,* Fumie Miki, and Kazuko Nagase


Illustration

Effects of ultrasonic wave on acid degradation of chitin ([N -acetyl- D -glucosamine]n ) were examined for the compositions of its first seven members (n=1-7 ) by HPLC. The yield of oligosaccharides increased almost in proportion of the sonolysis time up to 120 min. The yield of saccharides in the degradation fluid by concd HCl with sonolysis was about 2-4 times as much as that in the hydrolysis by HCl only.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1859-1861 (1995) [Vol. 68, No. 7, July, 1995]

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Direct Determination of the Intermolecular Pair-Potential Energy Function of Methane from the Extended Principal of the Corresponding States

Elaheh K. Goharshadi* and Ali Boushehri


Illustration

The pair potential-energy function for methane has been determined using a direct inversion of the experimental reduced viscosity collision intergrals obtained from a corresponding-states correlation. The potential obtained in this way is in reasonable agreement with the potential independently known from the crossed molecular-beam technique.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1863-1866 (1995) [Vol. 68, No. 7, July, 1995]

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Molecular Reorientation in AlBr3 .NH3 , as Studied by the 81 Br Nuclear Quadrupole Resonance

Hideta Ishihara,* Koji Yamada, Tsutomu Okuda, and Alarich Weiss


Illustration

In a crystal of AlBr3 .NH3 , a reorientation of the AlBr3 groups, or molecular tumbling, is executed at temperatures above 260 K according to the results of measurements of the temperature dependence of the NQR frequencies and spin-lattice relaxation times of 81 Br NQR.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1867-1872 (1995) [Vol. 68, No. 7, July, 1995]

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N , N -Dimethylformamide+2-Methoxyethanol Binary Mixtures. Viscosity and Activation Energy of Viscous Flow at Various Temperatures

Fulvio Corradini, GianCarlo Franchini, Andrea Marchetti, Mara Tagliazucchi, and Lorenzo Tassi*


Illustration

Dynamic viscosity ( ) of title binary mixtures has been investigated in the -10t/ °C80 temperature range, and some empirical relationships have been applied for fitting procedures. Furthermore, thermodynamics of viscous flow have been evaluated, and the excess mixing properties E and G*E provide evidence of the presence of solvent-cosolvent complex species.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1873-1882 (1995) [Vol. 68, No. 7, July, 1995]

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Formation of the Oxanickelacyclopentene Complex from Nickel(0), Carbon Dioxide, and Alkyne. An ab initio MO/SD-CI Study. Part II. Reactivity and Regioselectivity of Hydroxyacetylene

Shigeyoshi Sakaki,* Kazuya Mine, Taisuke Hamada, and Toru Arai


Illustration

Formation of oxanickelacyclopentene from Ni(0), carbon dioxide, and hydroxyacetylene was investigated with the ab initio MO/SD-CI method. Of two possible products, [(H3 P)Ni-C(OH)=CH-CO(O)] is yielded with a lower activation energy and a greater exothermicity than[(H3 P)Ni-CH=C(OH)-CO(O)]. Thisregioselectivity is discussed, together with the higher reactivity of hydroxyacetylene than that of acetylene.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1883-1888 (1995) [Vol. 68, No. 7, July, 1995]

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Pressure-Induced Phase Transition in the 1,2,4,5-Tetrabromobenzene Crystal

Fumio Shimizu, Yoshio Suzuki, Keiko Mitarai, Mitsuyo Fujino, Hiroshi Kawano, Yoshinori Nibu, Hiroko Shimada,* and Ryoichi Shimada


Illustration

The pressure effect on the Raman bands due to the inter- and intramolecular vibrations of the 1,2,4,5-tetrabromobenzene crystal indicates that the crystal undergoes the phase transition from the to phases under the pressure of about 0.7 GPa and the intermolecular repulsive interaction is fairly stronger in the 1,2,4,5-tetrabromobenzene crystal than in the 1,2,4,5-tetrachlorobenzene crystal.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1889-1895 (1995) [Vol. 68, No. 7, July, 1995]

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Kinetics of Electrochemical Reduction of Carbon Dioxide on a Gold Electrode in Phosphate Buffer Solutions

Hidetomo Noda, Shoichiro Ikeda,* Akio Yamamoto, Hisahiko Einaga, and Kaname Ito


Illustration

Kinetics of the formation of CO which is the principal product by electroreduction of CO2 on a Au electrode has been studied in a series of potassium phosphate buffer solutions. The Tafel slopes of the partial current density for the CO formation, ICO , at different pH are all ca. -120 mV/decade. A reaction mechanism has been proposed based on the relationships among ICO , the electrode potential, and the reaction order of CO2 , which is ca. 1.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1897-1903 (1995) [Vol. 68, No. 7, July, 1995]

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Ultraviolet Photoelectron Spectroscopy of Alkaline-Metal Doped Polyacetylene

Takayuki Miyamae,*, Koji Kamiya, Shinji Hasegawa, Kazuhiko Seki, Chizuko Tanaka, and Jiro Tanaka


Illustration

Alkaline-metal doped polyacetylenes (PA) were studied by ultraviolet photoelectron spectroscopy (UPS) using synchrotron radiation. The top of the valence band of trans -PA (a) exists at 0.9 eV below EF . At the intermediate doping (b), the position of EF was shifted toward Evac and a charged soliton state was found in the energy gap region. Ab initio MO calculation of interchain interaction gives a good description of the UPS spectra of heavily doped PA (c).

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1905-1914 (1995) [Vol. 68, No. 7, July, 1995]

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IR Investigation of Selective Reduction of NO by Ethene on Cu-ZSM-5

Takeshi Tabata,* Hirofumi Ohtsuka, Mikako Kokitsu, and Osamu Okada


Illustration

From IR investigation during SCR of NO using C2 H4 on Cu-ZSM-5, Peak I (maybe organic NOx ) was first observed, followed by Peak II (carbonyl) with production of N2 and N2 O, in the presence of adsorbed NO2 , gaseous C2 H4 and NO at 310 K. At 473 K, N2 and CO evolved rapidly with IR peaks of carboxylate, followed by Peak II.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1915-1919 (1995) [Vol. 68, No. 7, July, 1995]

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Segmented Contractions of Gaussian Basis Sets for Relativistic Molecular Calculations

Yoshihiro Watanabe and Osamu Matsuoka*


Illustration

A new segmented contraction scheme of relativistic Gaussian basis sets is proposed. It is similar to the contraction scheme adopted for nonrelativistic basis sets and is able to reproduce very well physical quantities computed using uncontracted basis sets.

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


Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1921-1927 (1995) [Vol. 68, No. 7, July, 1995]

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Micro Enzyme-Sensor with an Osmium Complex and Porous Carbon for Measuring Galactose

Kazuhisa Miyata,* Masahiko Fujiwara, Junko Motonaka, Toshihiro Moriga, and Ichiro Nakabayashi


Illustration

A micro sensor based on an osmium complex and porous carbon was prepared for measuring galactose. No membrane is required on the surface. The diameter of the sensor point is only 25 m. The sensor reaction scheme is shown below:

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1929-1933 (1995) [Vol. 68, No. 7, July, 1995]

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Synergistic Extraction of Rare Earths(III) with -Diketone and Nitrogen-Containing Terdentate Ligand, 2,2' :6' ,2'' -Terpyridine

Saeko Satake, Satoshi Tsukahara,* and Nobuo Suzuki

The extraction of rare earths(III) (RE: La, Sm, Tb, and Lu) was investigated using -diketone (HA), trifluoroacetylacetone or hexafluoroacetylacetone, with 2,2' :6' ,2'' -terpyridine (terpy) in benzene. Each RE(III) was extracted as 1 , and equilibrium constants were determined. The synergistic effect of terpy depended on -diketones and improved the separation efficiency among RE(III)s.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1935-1940 (1995) [Vol. 68, No. 7, July, 1995]

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Mssbauer Emission Spectra of 119 Sn in Binary Compounds of Antimony and Tellurium

Shizuko Ambe* and Fumitoshi Ambe

The Mssbauer emission spectra of defect 119 Sn atoms arising from 119 Sb and 119m Te were measured in the compounds listed below. The isomer shifts of defect and normal 119 Sn were shown to correlate with the electronegativity of ligands in binary compounds of the main-group elements of the periodic table. 119m Te119 Sb119 Sn* Mssbauer ray GaSb, InSb, In2 Te3 , ZnSb, CdSb, CdTe, and Ag2 Te

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1941-1945 (1995) [Vol. 68, No. 7, July, 1995]

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Kinetics and Mechanism of the High-Temperature Selenidization of Titanium

Haruo Naruke,* Kenji Yamada, Kazuyuki Kakegawa, and Yoshinori Sasaki


Illustration

The reaction of titanium sheet with selenium vapor gave a TiSe2 film on the metal. The reaction obeyed a parabolic rate law. Its rate constant (Kp ) was dependent on the temperature and was approximately proportional to the Se2 pressure (PSe2 ). The diffusing species of the reaction was found to be selenium.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1947-1954 (1995) [Vol. 68, No. 7, July, 1995]

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Kinetics and Mechanisms of Photoinduced Reduction of Methylviologen by N -Alkyltetraphenylporphyrinatozinc(II) in Methanol

Keiichi Tsukahara,* Naoko Sawai, Satoko Hamada, Takashi Nakazawa, and Ryoichi Nakagaki


Illustration

Photoinduced reduction of methylviologen by N -alkylporphyrinatozinc(II), [Zn(BrPrtpp)Cl], was studied in degassed methanol. Methylviologen radical cation accumulated in the presence of triethanolamine. Photophysical and photochemical properties of [Zn(BrPrtpp)Cl] were discussed and compared with those of [Zn(tpp)].

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1955-1958 (1995) [Vol. 68, No. 7, July, 1995]

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Kinetic Study of Interconversion between Two Geometrical Isomers of the Methoxy-Bridged Bis(silylene)iron Complex, ( -C5 Me5 )(OC)Fe{(SiMe2 )...OMe...(SiMeOMe)}

Keiji Ueno* and Hiroshi Ogino*


Illustration

Isomerization between two geometrical isomers of the methoxy-bridged bis(silylene)iron complex, anti - and syn -(5 -C5 Me5 )(OC)Fe{(SiMe2 )...OMe...(SiMeOMe)}, was investigated by means of a variable-temperature 1 H NMR experiment and a complete lineshape analysis. A concerted mechanism in which the bridging OMe group is replaced by the terminal OMe group is proposed for the isomerization.

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Articles
Orgainc and Biological
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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1959-1968 (1995) [Vol. 68, No. 7, July, 1995]

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Synthesis and Characterization of Hybrid Porphyrin Dimers and Halogenated Porphyrin Dimers

Kouji Iida, Mamoru Nango,* Kenichi Okada, Masaya Hikita, Mitsutaka Matsuura, Takayuki Kurihara, Takeharu Tajima, Ayako Hattori, Shinichi Ishikawa, Keiji Yamashita, Kazuichi Tsuda,* and Yukihisa Kurono


Illustration

Zinc hybrid porpyrin dimers and manganese(III) halogenated porphyrin dimers were synthesized. An efficient energy transfer in the zinc hybrid dimers and catalytic activities of transmembrane electron transfer by the manganese porphyrin dimers were observed, depending on the porphyrin structure.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1969-1979 (1995) [Vol. 68, No. 7, July, 1995]

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A Novel Dehydrative Ring-Transformation of 1-Alkyl-3-aroylpyrrolidines into 1-Alkyl-2-aryl-3-methylpyrroles

Shuntaro Mataka,* Hirohisa Kitagawa, Takehito Tsukinoki, Masashi Tashiro, Kazufumi Takahashi, and Kichinosuke Kamata


Illustration

When heated in ethylene glycol, 3-aroyl-1-alkylpyrrolidines, which are readily accesible via the condensation of amino acid, aldehyde, and 1-aryl-2-propen-1-one, underwent a novel ring-transformation, giving 1-alkyl-2-aryl-3-methylpyrroles. Bicyclic pyrroles were obtained by starting from cyclic amino acid.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1981-1987 (1995) [Vol. 68, No. 7, July, 1995]

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Novel C5-Substituted 2' -Deoxyuridine Derivatives Bearing Amino-Linker Arms: Synthesis, Incorporation into Oligodeoxyribonucleotides, and Their Hybridization Properties

Hiroaki Ozaki, Akiko Nakamura, Midori Arai, Masakazu Endo, and Hiroaki Sawai*


Illustration

2' -Deoxyuridine derivatives bearing several kinds of amino-linker arms at C5 position were synthesized from 5-(methoxycarbonylmethyl)-2' -deoxyuridine and incorporated into oligodeoxyribonucleotides by a phosphoramidite process. The amino-linker arm affected the stability of the duplexes depending on the number of amino groups in the linker arm and the length of the arm.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1989-1998 (1995) [Vol. 68, No. 7, July, 1995]

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A Membrane Protein Model: Polypeptides with Four -Helix Bundle Structure on 5,10,15,20-Tetrakis[2-(carboxymethoxy)phenyl]porphyrin

Toru Arai, Keisuke Kobata, Hisakazu Mihara, Tsutomu Fujimoto, and Norikazu Nishino*


Illustration

The atropisomerization of the title porphyrin was very rapid. Four -helix peptides, H-(QLLQALA)3 -NHCH2 CH2 OH, were connected to this porphyrin. This polypeptide-porphyrin hybrid showed high -helicity in methanol and in Tris.HCl buffer. Probably the helix bundle structure was formed on the porphyrin. This hybrid was successfully incorporated into the egg yolk lecithin vesicles.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 1999-2009 (1995) [Vol. 68, No. 7, July, 1995]

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Manganese(III)-Mediated Oxidative Radical Cyclization 2. Reaction of 1,1, , -Tetraarylsubstituted Terminal Alkadienes with Malonamide or Acetoacetamide

Hiroshi Nishino,* Hideaki Hashimoto, James D. Korp, and Kazu Kurosawa


Illustration

The oxidation of 1,1,6,6-tetraaryl-1,5-hexadienes with manganese(III) acetate in the presence of malonamide gave 3-azabicyclooctanes and 3,10-dioxatricycloundecanes in good to moderate yields. The selectivity of the inter- and intra-molecular cyclizations containing the carboxamide moiety of malonamide or acetoacetamide is discussed.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2011-2016 (1995) [Vol. 68, No. 7, July, 1995]

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Synthesis and Dynamic Stereochemistry of a Tri(1-azulenyl)methyl Cation Containing a Different Substituent on Each Azulene Ring

Shunji Ito, Noboru Morita, and Toyonobu Asao*


Illustration

The first example of a tri(1-azulenyl)methyl cation containing a different substituent on each azulene ring was synthesized, and the dynamic stereochemistry of the cation was studied by temperature-dependent 1 H NMR spectra, which supported the one-ring flip mechanism and the validity of the flip mechanism.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2017-2020 (1995) [Vol. 68, No. 7, July, 1995]

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A Novel Enzymatic Decarboxylation Proceeds via a Thiol Ester Intermediate

Takayasu Kawasaki, Masakatsu Watanabe, and Hiromichi Ohta*


Illustration

The mechanism of a novel decarboxylase (AMDase)-catalyzed decarboxylation reaction was proposed based on studies of the interaction of the enzyme with an active site-directed inhibitor, -bromophenylacetate. The inhibitory effect of this inhibitor indicated that the enzyme reaction proceeds via a thiol ester intermediate.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2021-2023 (1995) [Vol. 68, No. 7, July, 1995]

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Effect of a Liquid-Liquid Phase Separation on the Slopes of Density vs. Concentration Plots

Isamu Inamura,* Yuji Jinbo, Yoriko Akiyama, and Yasuo Kubo


Illustration

The densities were measured for polymer(1)-polymer(2)-water(3) systems. In all cases, the linear relationship of the density vs. concentration plots was not affected by the occurrence of a liquid-liquid phase separation.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2025-2031 (1995) [Vol. 68, No. 7, July, 1995]

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Preparation and Chemical Reactions of Trifluoroacetaldehyde Azine (1,1,1,6,6,6-Hexafluoro-3,4-diaza-2,4-hexadiene)

Akihito Hashidzume, Atsushi Kajiwara, Akira Harada, Mikiharu Kamachi,* and Masami Kusunoki


Illustration

Trifluoroacetaldehyde azine (TFAcAz) was prepared and its chemical reactivity was investigated. The reaction of TFAcAz with triethylamine gave a cyclic dimer containing a 1,4-dihydro-1,2,4,5-tetrazine ring; those with methanol and water provided 1,2-adducts.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2033-2041 (1995) [Vol. 68, No. 7, July, 1995]

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Studies of the Selective O -Alkylation and Dealkylation of Flavonoids. XVIII. A Convenient Method for Synthesizing 3,5,6,7-Tetrahydroxyflavones

Tokunaru Horie,* Takashi Kobayashi, Yasuhiko Kawamura, Isao Yoshida, Hideaki Tominaga, and Kazuyo Yamashita


Illustration

In the demethylation of the flavones, the effect of reagents against substrates were elucidated and a new convenient method for synthesizing the title compounds was established.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2043-2051 (1995) [Vol. 68, No. 7, July, 1995]

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Direct CC Triple Bond Formation from the C=C Double Bond and Direct Hydroxylation into the o -Position of a Nitro Group on the Benzene Nucleus with Potassium t -Butoxide in N , N -Dimethylformamide in the Air

Shuzo Akiyama,* Kunihiko Tajima, Shin'ichi Nakatsuji, Kenichiro Nakashima, Kazuko Abiru, and Miwa Watanabe


Illustration

A novel and facile direct CC bond formation from the C=C bond of various styryl compounds has been found by treatment of t -BuOK in DMF in the air. Moreover, in 4-substituted 4' -nitrostilbenes and their vinylogs, direct hydroxylation into ortho-position of a nitro group on the benzene nucleus was observed.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2053-2060 (1995) [Vol. 68, No. 7, July, 1995]

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Hafnium(IV) Trifluoromethanesulfonate, An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reactions

Iwao Hachiya, Mitsuhiro Moriwaki, and Sh Kobayashi*


Illustration

Hafnium(IV) trifluoromethanesulfonate (hafnium(IV) triflate, Hf(OTf)4 ) was synthesized from hafnium tetrachloride and trifluoromethanesulfonic acid. The triflate thus prepared was found to be effective in the catalytic Friedel-Crafts acylation and alkylation reactions in lithium perchlorate-nitromethane (LiClO4 -MeNO2 ).

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Articles
Applied and Materials
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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2061-2065 (1995) [Vol. 68, No. 7, July, 1995]

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Studies on the Complex Formation between Iron(III) or Copper(II) and Poly(vinyl alcohol) in Terms of Inclusion of the Metal Hydroxide-Like Clusters by the Polymer

Hiroshi Yokoi,* Yasuyoshi Mori, and Yutaka Fujise


Illustration

Poly(vinyl alcohol) forms inclusion-type complexes with iron(III) hydroxide-like clusters through a hydrophobic interaction. The clusters are ca. 30 in size and comprise about 120 Fe atoms. Poly(vinyl methyl ether) also forms analogous complexes.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2067-2072 (1995) [Vol. 68, No. 7, July, 1995]

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Study on the Interaction between Iron(III) Hydroxide Oxide and Cation Exchange Resins

Ichiro Inami* and Takao Baba


Illustration

Cation exchange resins used for more than five years (resins C and D) showed high adsorption efficiency to amorphous iron hydroxide oxide. This phenomenon is ascribed to the expansion of micropores, induced by oxidative swelling.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2073-2081 (1995) [Vol. 68, No. 7, July, 1995]

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Formalized Drawing of Fullerene Nets. 1. Algorithm and Exhaustive Generation of Isomeric Structures

Mitsuho Yoshida and Eiji sawa*


Illustration

A novel formalism to draw net diagrams of fullerenes that uses Drer's old design is proposed. The method is useful not only in making paper models of any desired fullerenes in a systematic way but also in exhaustive enumeration of isomeric fullerens. Convenient programs are provided.

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Copyright (C) 1995 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 68, 2083-2092 (1995) [Vol. 68, No. 7, July, 1995]

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Formalized Drawing of Fullerene Nets. 2. Applications to Mapping of Pyracylene Rearrangements, C2 -Insertion/Elimination Pathways, and Leapfrog/Carbon Cylinder Operations

Mitsuho Yoshida and Eiji sawa*


Illustration

Using net drawings of fullerenes on triangular or hexagonal lattice, skeletal transformations of fullerenes as given in the title are traced exhaustively and systematically. Unexpectedly stable anti-IPR isomers are found. Preferential formation of C84 and C90 is predicted.

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