Bulletin of the Chemical Society of Japan - Vol. 77, No. 12 (December, 2004)

Bulletin of the Chemical Society of Japan
Vol. 77, No. 12 (December, 2004)

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Web Release Date: December 10, 2004

2129-2146 Recent Advances in the Synthesis of trans-Fused Polycyclic Ethers by Hydroxy-Epoxide-Cyclization and Ether-Ring-Expansion Reactions
K. Fujiwara^* and A. Murai^*
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In this review, recent advances in the synthesis of trans-fused polycyclic ethers by hydroxy-epoxide-cyclization reactions via monocyclic epoxonium ion intermediates and ether-ring-expansion reactions via bicyclic epoxonium ion intermediates are described.

Web Release Date: December 10, 2004

2147-2157 “Syn-Effect” in the Conversion of (E)-α,β-Unsaturated Esters into the Corresponding β,γ-Unsaturated Esters and Aldehydes into Silyl Enol Ethers
S. K. Guha, A. Shibayama, D. Abe, M. Sakaguchi, Y. Ukaji,^* and K. Inomata^*
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The stereochemistry in the conversion of (E)-α,β-unsaturated esters into β,γ-unsaturated esters and aldehydes into silyl enol ethers was investigated. The Z-selectivity of the products was rationalized by the “syn-effect”, which is attributed primarily to the σ → π* interaction.

Web Release Date: December 10, 2004

2159-2164 Two-Dimensional ¹H Spin-Exchange NMR Study of Molecular Arrangements in Diphenylhexatrienes
S. Hayashi^* and Y. Sonoda
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Methoxy derivative demonstrates intermolecular spin exchange between triene protons and methoxy protons. Thus, a methoxy group is located close to a hexatriene chain of an adjacent molecule. For formyl derivative, there are no indications of intermolecular spin exchange.

Web Release Date: December 10, 2004

2165-2171 Structural Evidence for an Independent Inclusion of Hexyl and Octyl Chains of Hexyldimethyloctylammonium Bromide in an α-Cyclodextrin Cavity
N. Funasaki,^* K. Yamauchi, S. Ishikawa, and S. Hirota
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NMR chemical-shift data indicate that the hexyl and octyl chains of hexyldimethylammonium bromide are independently incorporated in an α-cyclodextrin cavity.

Web Release Date: December 10, 2004

2173-2178 Photoionization and Ion Pair Formation of N,N-Diethyl-p-phenylenediamine in Various Polar Solvents
Y. Hirata^* and O. Kawashima
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In addition to the biphotonically formed geminate pair, the dissociation of the monophotonically produced long-lived ion pair is observed. The long lifetime of the ion pair indicates that not only the Coulombic interaction but also the exciplex-like interaction is important.

Web Release Date: December 10, 2004

2179-2183 Bond-Length Equalization and Aromaticity in Charged π-Systems
J. Aihara
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The conventional interpretation of bond-length equalization gives a misleading picture of the aromaticity of charged π-systems. Charged π-systems may be antiaromatic even if they have no bond-length alternation.

Web Release Date: December 10, 2004

2185-2188 The Photovoltaic Mechanism of a Polythiophene/Perylene Pigment Two-Layer Solar Cell
J. Nakamura, S. Suzuki, K. Takahashi,^* C. Yokoe, and K. Murata
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The energy conversion efficiency of a two-layer organic solar cell consisting of a perylene pigment and regioregular polythiophene polymer was 0.99% under illumination with simulated solar light (AM 1.5–100 mW cm⁻²).

Web Release Date: December 10, 2004

2189-2191 A Non-Born–Oppenheimer Effective Hamiltonian for the Analysis of Vibrational–Rotational and Rotational Spectra of Diatomic Molecules
H. Uehara
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A non-Born–Oppenheimer effective Hamiltonian for diatomic molecules expressed with the optimal fitting parameters of Born–Oppenheimer corrections has been derived. It provides a clear-cut understanding of the determinable correction parameters.

Web Release Date: December 10, 2004

2193-2198 Kinetics on Isomeric Alcohols Recognition by α- and β-Cyclodextrins Using Ultrasonic Relaxation Method
T. Fukahori, S. Nishikawa,^* and K. Yamaguchi
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The complexation reaction between α-, or β-cyclodextrin and several isomeric alcohols in water was studied kinetically by ultrasonic absorption method. The rate and thermodynamic constants on the inclusion reaction were discussed in relation to the structure of the host and guest molecules.

Web Release Date: December 10, 2004

2199-2202 A Structural Phase Transition and Molecular Motions in (C₂H₅NH₃)₂[ZnBr₄] Studied by ¹H NMR and X-ray Diffraction
K. Horiuchi,^* C. Iijima, S. Miyagi, H. Yogi, T. Fukami, and R. Ikeda
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The crystal undergoes a 1st order structural phase transition at T_c = 300 K, which is driven by the disordering of cationic orientations. The crystal structure at 295 K was determined to be orthorhombic with space group of P2₁2₁2₁.

Web Release Date: December 10, 2004

2203-2204 Electron-Transfer Kinetics of Nitroxide Radicals as an Electrode-Active Material
T. Suga, Y.-J. Pu, K. Oyaizu, and H. Nishide^*
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The electron-transfer rate constants of nitroxide derivatives, 4-(N-t-butyl-N-oxylamino)-t-butylbenzene, 4-(N-t-butyl-N-oxylamino)methoxybenzene, and 2,2,6,6-tetramethylpiperidinyl-N-oxyl, were investigated by electrochemical methods, which demonstrated that these radicals can potentially be used as a high power-rate electrode-active material due to their fast electron-transfer process.

Web Release Date: December 10, 2004

2205-2211 Synthesis and Characterization of Polynuclear Chain and Tetranuclear Complexes of Mixed-Valent Ruthenium(II,III) Pivalate with N,N′-Didentate Ligands
D. Yoshioka, M. Mikuriya,^* and M. Handa^*
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[Ru₂(piv)₄L]_n(BF₄)_n (Hpiv = pivalic acid, L = pyrazine (1), 4,4′-bipyridine (2), 1,4-diazabicyclo[2.2.2]octane (3), and phenazine (4)), [Ru₂(piv)₄(H₂O)₂(tetramethylpyrazine)]_n(BF₄)_n·nCH₂Cl₂ (6), and [{Ru₂(piv)₄(H₂O)}₂(phenazine)](BF₄)₂ (5), were synthesized and characterized by measurements of the infrared and electronic spectra, and the temperature dependence of the magnetic moments.

Web Release Date: December 10, 2004

2213-2218 Optimal Environment for Maximal Molecular Recognition against Temperature. Three Distinct Patterns in Temperature–Recognition Profiles as a Function of Composition of Aqueous Binary Solvents
T. Endo,^* K. Sugio, S. Kogure, S. Horikosi, M. Tojima, Y. Aono, and M. M. Ito
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Aqueous mixed solvents in the medium region of mole fraction of water are indispensable for maximal recognition (the presence of a maximum in the temperature–selectivity relationship) to occur against temperature.

Web Release Date: December 10, 2004

2219-2229 A New Synthetic Method for Dipeptides Containing α,β-Didehydroamino Acids Utilizing an α-Tosylglycine Residue
Y. Shiraishi, H. Yamauchi, T. Takamura, and H. Kinoshita^*
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The reaction of dipeptides containing an N-Boc- or N-Z-tosylglycine residue with a nitro compound followed by treatment with base or with aldehyde in the presence of base and tributylphosphine afforded the corresponding dipeptide containing an α,β-didehydroamino acid residue with (Z)-configuration predominantly.

Web Release Date: December 10, 2004

2231-2235 An Effective System to Synthesize Hypolipidemic Active α-Asarone and Related Methoxylated (E)-Arylalkenes
A. Sharma, B. P. Joshi, and A. K. Sinha^*
[Full Text PDF(J-STAGE)]

Methoxylated (E)-arylalkenes (1a–1k) were prepared in two steps by an improved Grignard reaction comprising the reverse addition of alkylmagnesium halide to benzaldehydes (2a–2k) in anhydrous ether and toluene into arylalkanols (3a–3k) in high yield, followed by dehydration with silica gel under microwave irradiation for 3–12 min, depending upon the substituents attached to the aromatic ring to afford hypolipidemic active α-asarone (1a) and related methoxylated (E)-arylalkenes (1b–1k).

Web Release Date: December 10, 2004

2237-2250 Selective Oxidative Carbonylation of Amines to Oxamides and Ureas Catalyzed by Palladium Complexes
K. Hiwatari, Y. Kayaki, K. Okita, T. Ukai, I. Shimizu,^* and A. Yamamoto^*
[Full Text PDF(J-STAGE)]

The palladium-catalyzed oxidative carbonylation of amines produced oxamides and ureas selectively by using 1,4-dichloro-2-butene (DCB) or I₂ as oxidants. The carbonylation mechanisms are discussed based on fundamental studies of carbamoylpalladium complexes as model intermediates.

Web Release Date: December 10, 2004

2251-2255 Photocatalytic Oxidation of Alkanes with Dioxygen by Visible Light and Copper(II) and Iron(III) Chlorides: Preference Oxidation of Alkanes over Alcohols and Ketones
K. Takaki,^* J. Yamamoto, K. Komeyama, T. Kawabata, and K. Takehira
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Partial oxidation of alkanes with dioxygen was effectively induced by visible light/CuCl₂ or FeCl₃ catalyst system. Particularly with the copper catalyst, alkanes were oxidized faster than the alcohols and ketones generated, and faster than benzylic compounds.

Web Release Date: December 10, 2004

2257-2263 Synthesis of Chroman Derivatives by the Ring Expansion Reaction of Spirodienones, and an Assessment of their Plant Growth Inhibition
F. Doi, T. Ohara, T. Ogamino, K. Higashinakasu, K. Hasegawa, and S. Nishiyama^*
[Full Text PDF(J-STAGE)]

In the selective conversion of spirodienone derivatives electrochemically synthesized into the corresponding chroman derivatives, an electrolytic effect of the 4-(3-hydroxypropyl)phenols carrying the methyl, halogen, and trifluoromethyl groups at the ortho position regulated the direction of the rearrangement. Several synthesized chromans, were submitted to plant growth-inhibitory assessments against cress and oat.

Web Release Date: December 10, 2004

2265-2267 A New Route to 2,4,6-Trisubstituted-6H-1,3-Oxazines
M. Kidwai,^* R. Thakur, and R. Mohan
[Full Text PDF(J-STAGE)]

A new route towards an environmentally benign synthesis of the title compounds has been developed using montmorillonite K-10 clay as catalyst under microwave irradiation (MWI).

Web Release Date: December 10, 2004

2269-2272 Asymmetric Transformation of Enones with Synechococcus sp. PCC 7942
K. Shimoda,^* N. Kubota, H. Hamada, S. Yamane, and T. Hirata
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Asymmetric transformations of s-trans enones with the endocyclic C–C double bond and of s-cis enones with the exocyclic C–C double bond by Synechococcus sp. PCC 7942 proceeded with excellent enantioselectivity to give optically active α-substituted (S)-ketones and minor (S)-alcohols under illumination.

Web Release Date: December 10, 2004

2273-2281 Synthesis and Stereochemistry of N-Phenyl-N-9-triptycylhydroxylamine Derivatives and Related Compounds
C. Agawa, K. Otsuka, M. Minoura, Y. Mazaki, and G. Yamamoto^*
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Stereochemistry of the title compounds was studied by X-ray crystallography and dynamic NMR spectroscopy. Energy barriers to conformational interconversion were elucidated.

Web Release Date: December 10, 2004

2283-2288 A Water-Soluble Phospholipid Polymer as a New Biocompatible Synthetic DNA Carrier
S. Sakaki,^* M. Tsuchida, Y. Iwasaki, and K. Ishihara
[Full Text PDF(J-STAGE)]

The phospholipid polymer, poly[2-methacryloyloxyethyl phosphorylcholine (MPC)-co-2-aminoethyl methacrylate (AEMA)] (poly(MPC-co-AEMA)) is a useful water-soluble polymer which can form a complex with DNA which can assist in DNA delivery into the cell.

Web Release Date: December 10, 2004

2289-2290 A Novel Method for Preparing PEMFC Catalytic Layers
J. Zhang, X. Wang, J. Hu, B. Yi, and H. Zhang^*
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A novel PEMFC catalytic layer is fabricated by partial pyrolyzing of Nafion. The Nafion without the sulfonic acid group serves as a hydrophobic material, and the unpyrolyzed species acts as a proton conductor in the catalytic layer.