bluuebunny/crossref_metadata_2025 huggingface dataset:
NEW METAL CATION-SELECTIVE IONOPHORES DERIVED FROM CALIXARENES
Authors: Chang Suk-Kyu , Cho Iwhan
Published: July 2006

Ethoxycarbomethyl derivatives of calix[6]arene and calix[8]arene prepared by the reaction of bromoacetic acid ester with the calixarenes exhibited distinct size-selectivity in their ion-extracting behaviors towards Cs+ and K+ ions.
CRYSTALLINE COMPLEXES OF CYLINDRICAL MACROCYCLIC POLYETHERS. DIDECALINO- AND DECALINO-BENZO-18-CROWN-6
Authors: Kobiro Kazuya , Kakiuchi Kiyomi , Tobe Yoshito , Odaira Yoshinobu
Published: July 2006

Didecalino- and decalino-benzo-18-crown-6 have been found to form 1:1 (crown ether:cation mole ratio) complexes in stoichiometry with NaNCS, KNCS, RbNCS, CsI3, and/or H3OClO4 without any formation of sandwich-type complexes.
TOTAL SYNTHESES OF MOKKO LACTONE, DEHYDROCOSTUS LACTONE, AND EREMANTHIN
Authors: Ando Masayoshi , ONO Akio , Takase Kahei
Published: July 2006

A series of guaianolides such as mokko lactone, dehydrocostus lactone, and eremanthin which posses a common structural unit in A ring have been synthesized from 1-oxoeudesm-2-eno-13,6α-lactone in 7 steps. The key step involves solvolytic rearrangement of 1β-mesyloxyeudesm-4(14)-eno-13,6α-lactone.
BONDING ISOMERS OF TRIORGANOSTANNYL ENOLATES ANALYZED BY 119Sn NMR SPECTROSCOPY
Authors: Kobayashi Kazuko , Kawanisi Mituyosi , Hitomi Torazô , Kozima Sinpei
Published: July 2006

The bonding isomers of triorganostannyl enolates were analyzed by 119Sn NMR spectroscopy. In some cases the existence of an equilibrium between the O-stannyl enolate and C-stannyl derivative was confirmed by variable temperature 119Sn NMR spectra.
BORON HYDRIDES AS TEMPLATES FOR HYDROAZULENE SYNTHESIS
Authors: Stevenson J W S , Bryson T A
Published: July 2006

Boron annulation (hydroboration and carbonylation or equivalent technique) of 1,5-dienes forms hydroazulene systems which are prototypes of pseudoguaianolides.
CRYSTAL STRUCTURE OF cis-DIAMMINEPLATINUM α-PYRROLIDONE VIOLET, [Pt4(NH3)8(C4H6NO)4](PF6)2(NO3)2.56·5H2O
Authors: Matsumoto Kazuko , Fuwa Keiichiro
Published: July 2006

Crystal structure of cis-diammineplatinum α-pyrrolidone violet, [Pt4(NH3)8(C4H6NO)4](PF6)2(NO3)2.56·5H2O is reported. From the results of X-ray diffraction analysis and potentiometric oxidative titration, it has been found that the compound is nonstoichiometric, being a mixture of 44% of [Pt4(NH3)8(C4H6NO)4]4+ and 56% of [Pt4(NH3)8(C4H6NO)4]5+ with the average platinum oxidation state of 2.14.
X-RAY CRYSTAL STRUCTURE OF [N,N′-ETHYLENEBIS(PYRROL-2-YLMETHYLENEAMINATO)]NICKEL(II) COMPLEX
Authors: Kabuto Chizuko , Kikuchi Takemitsu , Yokoi Hiroshi , Iwaizumi Masamoto
Published: July 2006

The 1:1 complex of nickel (II) with N,N′-ethylenebis (pyrrol-2-ylmethyleneamine) in benzene-inclusion crystals is a planar complex with a highly strained geometry of coordination, as shown by X-ray structural analysis.
UNUSUAL 1:1 MOLECULAR COMPLEXES OF 2,5-DIARYL-1,4-DITHIINS WITH 2,4-DIARYLTHIOPHENES
Authors: Kobayashi Keiji , Iwasaki Fujiko
Published: July 2006

The title compounds have been found to form the crystalline 1:1 molecular complexes wherein distinct intermolecular interaction such as hydrogen bonding, charge transfer interaction, or clathrate inclusion was not found as studied by an X-ray analysis.
CUPRIC ION-CATALYZED DIOXYGENATION OF 1,2-CYCLOHEXANEDIONES. A NONENZYMATIC ANALOG FOR QUERCETINASE DIOXYGENATION
Authors: Utaka Masanori , Hojo Makoto , Fujii Yasuyuki , Takeda Akira
Published: July 2006

1,2-Cyclohexanediones were found to be dioxygenated by molecular oxygen with the aid of cupric ion to afford 1,5-keto acids and carbon monoxide. The reaction proceeds possibly via an endoperoxide intermediate. Methyl α-hydroxyadipates were also formed as byproducts. The mechanism of oxygenation is discussed.
ETHYLENE HYDRATION OVER NIOBIC ACID CATALYSTS
Authors: Ogasawara Kazuharu , Iizuka Tokio , Tanabe Kozo
Published: July 2006

Niobic acids preheated in vacuo at moderate temperatures (200–220 °C) were found to be highly active for ethylene hydration to form ethyl alcohol. The activity at steady state was higher than that of a well known solid phosphoric acid, the selectivity being more than 97% at a reaction temperature of 220 °C.
SUPERBASICITY OF RUBIDIUM OXIDE AND CAESIUM OXIDE, AND THEIR REACTION PROFILES OF ISOMERIZATION OF BUTENES
Authors: Tsuchiya Susumu , Takase Shigeyuki , Imamura Hayao
Published: July 2006

The superbasic sites on a rubidium oxide and a caesium oxide have been revealed by means of the benzoic acid titration method. The double-bond-migration and the cis–trans isomerization of butenes took place over the rubidium oxide and the caesium oxide; but the skeletal isomerization was not observed.
REGIO- AND STEREO-SELECTIVITIES IN THE TITANIUM COMPLEX CATALYZED HYDROBORATION OF CARBON–CARBON DOUBLE BONDS IN VARIOUS UNSATURATED COMPOUNDS
Authors: Lee Hyung Soo , Isagawa Kakuzo , Toyoda Hiromu , Otsuji Yoshio
Published: July 2006

The titanium complex prepared from TiCl3 and NaBH4 in THF in the presence of 18-crown-6 promotes the catalytic hydroboration of carbon–carbon double bonds in alkenes, alkadienes and unsaturated ethers with NaBH4, giving sodium organoborates which can be converted into alcohols by oxidation with H2O2/CH3ONa. The reaction proceeds with high regio- and stereo-selectivities.
A SIMPLE SYNTHESIS OF (1R and 1S)-[1-2H1]-1,5-ANHYDRO-d-GLUCITOL AND [1-2H2]-1,5-ANHYDRO-d-GLUCITOL
Authors: Funabashi Masuo , Yoshioka Shigetake
Published: July 2006

As a basic study of metabolism of 1,5-anhydro-d-glucitol, which has recently been identified in both human cerebrospinal fluid and plasma, the title compounds were conveniently synthesized as preliminary targets not only for multideuteration but for tritium labelling.
EFFECTS OF ALKALI METAL HALIDES IN THE FORMATION OF ALCOHOLS FROM CO AND H2 OVER SILICA-SUPPORTED MOLYBDENUM CATALYSTS
Authors: Tatsumi Takashi , Muramatsu Atsushi , Tominaga Hiro-o
Published: July 2006

Silica-supported molybdenum catalysts, promoted by alkali metal halides, give C1–C5 alcohols with good selectivity (up to 72% by weight of the total product, exclusive of CO2) from a CO–H2 mixture at 16 kg/cm2 and 260–300 °C.
SYNTHESIS OF CEMBRA-3E,7E,11E,15(17)-TETRAEN-cis-16,2-OLIDE
Authors: Aoki Mario , Uyehara Tadao , Kato Tadahiro
Published: July 2006

The titled natural product was synthesized from 3,7,11-trimethyl-cyclotetradeca-2E,6E,10E-trienone.
RATE CONSTANTS AND THERMODYNAMIC PARAMETERS FOR THE INCLUSION REACTIONS OF SOME p-HYDROXYPHENYLAZO DERIVATIVES OF SULFANILIC ACID WITH α-CYCLODEXTRIN
Authors: Yoshida Noboru , Seiyama Akitoshi , Fujimoto Masatoshi
Published: July 2006

Inclusion reactions of the title azo compounds with α-cyclodextrin were studied in aqueous solution by means of the stopped-flow method. The forward rate constants for the inclusion reactions were found to be in the order of magnitude 102–104 mol−1 dm3 s−1 Activation parameters were first determined for α-cyclodextrin system.
ON THE JAHN–TELLER SPLITTING FOR THE 2T2 STATE OF CH4+
Authors: Shiromaru Haruo , Takeshita Kouichi , Katsumata Shunji
Published: July 2006

The magnitude of the Jahn–Teller splitting of the 2T2 ionic state of methane was successfully calculated without determining the potential surface of the ionic state. This method can be easily applied to analyses of Jahn-Teller splittings observed in photoelectron spectroscopy.
SYNTHESIS OF (±)-ANASTREPHIN AND (±)-EPIANASTREPHIN
Authors: Saito Akira , Matsushita Hajime , Kaneko Hajime
Published: July 2006

(±)-Anastrephin and (±)-epianastrephin, sex and aggregation pheromenes of Caribbean and Mexican fruit flies, were synthesized by acid-catalyzed cyclization of 10-hydroxy-4,8-dimethyldeca-(3E,8E)-3,8-dienoic acid in 67% yield as a 1:1 mixture.
SELECTIVE FORMATION OF ISO-BUTENE FROM CARBON MONOXIDE AND HYDROGEN OVER ZIRCONIUM OXIDE CATALYST
Authors: Maehashi Tatsuichi , Maruya Ken-ichi , Domen Kazunari , Aika Ken-ichi , Onishi Takaharu
Published: July 2006

Iso-butene was selectively produced from CO–H2 reaction over ZrO2 catalyst under moderate conditions (0.5–21 atm, 300–450 °C).
SEPARATION AND CHARACTERIZATION OF TWO COBALT(III) DIASTEREOMERS DUE TO CHIRAL O-BONDED SULFINATE
Authors: Yamahari Kazuaki , Shimura Yoichi
Published: July 2006

Two diastereomers due to the chiral O-bonded sulfinate in Λ-[Co(NH2CH2CH2SO2-N,O)(en)2](ClO4)2 were separated and characterized by the visible-UV absorption, circular dichroism(CD), and 13C NMR spectra. The absolute configurations were determined by comparison of the CD spectra with that of the corresponding O-bonded Λ-R-seleninato complex. The racemization of the chiral sulfinato moiety proceeded at a relatively slow rate, which is responsible for the successful separation of the diastereomers.
A NEW SYNTHESIS OF trans-2-SUBSTITUTED-2-BUTENE-1,4-DIOLS FROM 2-BUTYNE-1,4-DIOL VIA NUCLEOPHILIC ADDITION OF GRIGNARD REAGENTS
Authors: Ishino Yoshio , Wakamoto Kohji , Hirashima Tsuneaki
Published: July 2006

trans-2-Substituted-2-butene-1,4-diols were readily obtained by reactions of 2-butyne-1,4-diol with Grignard reagents in good yields.
REGIOSELECTIVE FUNCTIONALIZATION OF cis-BICYCLO|3.3.0|OCTENONE DERIVATIVES. OXYMERCURATION/REDUCTION versus HYDROBORATION/OXIDATION. ACETAL GROUPS AS REGIO- AND STEREOSELECTIVE CONTROL ELEMENTS
Authors: Carceller Elena , Castelló Assumpta , García M Lluísa , Moyano Albert , Serratosa Félix
Published: July 2006

Cyclic acetal groups at the position 8 of the cis-bicyclo|3.3.0|octane system may act as regio- and stereoselective control elements, respectively, in hydroboration and oxymercuration reactions. Whereas the regioselectivity observed in hydroborations must be ascribed to homoallylic inductive effects, and leads predominantly to exo, 1,3-bifunctional relationships, the effect of acetal group in oxymercuration is mainly stereoselective due to coordination of mercury acetate with the nonbonding electron pairs of the endo-oxygen atom of the acetal group, and leads predominantly to exo, 1,4-bifunctional relationships.
SIPHONODIOL, A NEW POLYACETYLENIC METABOLITE FROM THE SPONGE SIPHONOCHALINA TRUNCATE
Authors: Tada Haruhiko , Yasuda Fumio
Published: July 2006

A new C23 polyacetylene diol was isolated from the marine sponge S. truncata and its structure was elucidated mainly on the basis of its spectral data.
TRIMETHYLSILYL TRIFLATE-CATALYZED REACTION OF BIS(METHYLTHIOMETHYL)AMINES WITH DIKETENE SILYL ACETALS. NOVEL CYCLIZATION LEADING TO FIVE- TO SEVEN-MEMBERED ALICYCLIC AMINES
Authors: Miyazawa Shuhei , Ikeda Kiyoshi , Achiwa Kazuo , Sekiya Minoru
Published: July 2006

Bis(methylthiomethyl)amines have been shown to react with diketene silyl acetals in the presence of trimethylsilyl triflate catalyst to give five- to seven-membered alicyclic amines.
PREPARATION AND SPECTROSCOPY OF THE FIRST Ru(IV) METHYL COMPLEXES, Ru(CH3)2(1-3:6-7:10-12-η-C12H18) and Ru(CH3)I(1-3:6-7:10-12-η-C12H18)
Authors: Nagashima Hideo , Ohshima Toshiyuki , Itoh Kenji
Published: July 2006

The first Ru(IV) methyl complexes, Ru(CH3)2(1-3:6-7:10-12-η-C12H18) and Ru(CH3)I(1-3:6-7:10-12-ηC12H18), are Prepared by organometallic methylation of RuCl2(1-3:6-7:10-12-η-C12H18).
REDUCTIVE ELIMINATION OF A Ru(IV) ALKYL COMPLEX PROMOTED BY NEUTRAL LIGANDS
Authors: Nagashima Hideo , Ohshima Toshiyuki , Itoh Kenji
Published: July 2006

Treatment of Ru(CH3)I(1-3:6-7:10-12-η-C12H18) with CO, tBuNC, or phosphites facilitates reductive coupling of the methyl group and the π-allyl moiety to give Ru(II) complexes, RuIL3(1-3-η-C13H21) [L=CO, tBuNC,P(OR)3]. Addition of one equivalent of tBuNC leads to selctive formation of Ru(tBuNC)I(1-3:6-7:11-12-η-C13H21).
SYNTHESIS AND PROPERTIES OF OLIGOADENYLIC ACIDS CONTAINING 2′-5′ PHOSPHORAMIDE LINKAGE
Authors: Sawai Hiroaki
Published: July 2006

Oligoadenylic acids containing 2′-5′ phosphoramide linkage were prepared by poly (U) template-directed condensation. Some of their properties are described.
A NEW ELECTROLYSIS METHOD. MAGNETOELECTROLYSIS
Authors: Iwakura Chiaki , Kitayama Masahiro , Edamoto Toshiyuki , Tamura Hideo
Published: July 2006

A fundamental work was carried out on the development of a new electrolysis method using a rotating cell and a permanent magnet. As a result, it was proved that the rotation of the conducting cell in an external magnetic field can induce a dc potential difference by which electrochemical reactions are directly brought about.
A DYNAMICAL PROFILE OF METAL INCORPORATION TO A LIPOSOMAL MEMBRANE AS STUDIED BY ELECTRON SPIN RESONANCE
Authors: Ishikawa Yuji , Tajima Kunihiko , Mukai Kazuo , Ochi Osamu , Ishizu Kazuhiko , Sakurai Hiromu
Published: July 2006

An Egg-Yolk lecithin liposome containing the surfacant cyclic polyamine was prepared, and a dynamical behavior of its Cu(II) ion uptake was studied by monitoring a time dependent decay of the isotropic copper nucleus hyperfine splitting in the ESR upon metal incorporation into a liposomal membrane. The reaction kinetics studied by ESR justified the fact that there are the two kinds of metal binding processes, in which the distinctive time course and the activation energy can be clearly demonstrated.
A NOVEL DIRECT SYNTHESIS OF AMIDINES FROM CARBOXYLIC ACIDS AND AMINES USING POLYPHOSPHORIC ACID TRIMETHYLSILYL ESTER (PPSE) AS CONDENSING AGENT
Authors: Kakimoto Masa-aki , Ogata Shin-ichi , Mochizuki Amane , Imai Yoshio
Published: July 2006

It was found that amidines were obtained directly by the reaction of carboxylic acids with amines in the presence of PPSE, and the yields of amidines were dependent on the structure of amines rather than that of carboxylic acids.
ENDOR DETERMINATION OF PROTON HYPERFINE SPLITTING CONSTANTS OF AMINOXYL RADICALS FREQUENTLY USED IN SPIN-PROBE-SPIN-LABEL METHOD
Authors: Kotake Yashige , Kuwata Keiji
Published: July 2006

ENDOR technique was applied to the determination of the accurate hyperfine splitting constants of protons in several aminoxyl radicals which are frequently used in spin-probe-spin-label method. The result was compared with that of NMR in the concentrated solution of the radicals. The magnitude of hyperfine splitting constants is shown to be very sensitive to the structure of the radical.
19F NMR CHEMICAL SHIFT IMAGING OF ANESTHETICS IN MODEL MEMBRANES
Authors: Kanazawa Yoko , Higuchi Wakako
Published: July 2006

The images of fluorinated anesthetics in the lipid dispersions were obtained by 19F NMR method using a commercial spectrometer with a satisfactory resolution in space and molecular species.
APPLICATION OF BIS(p-METHOXYPHENYL)SELENOXIDE AS AN OXIDIZING AGENT OF KORNBLUM OXIDATION
Authors: Ariyoshi Kimio , Aso Yoshio , Otsubo Tetsuo , Ogura Fumio
Published: July 2006

The title selenoxide was found to serve as a suitable agent for Kornblum oxidations of various benzyl bromides to the corresponding carbonyl compounds. On the other hand, the analogous sulfoxide and telluroxide hardly promoted such oxidations.
ELECTROGENERATED ACID AS AN EFFICIENT CATALYST FOR CYANATION OF ACETALS WITH TRIMETHYLSILYL CYANIDE
Authors: Torii Sigeru , Inokuchi Tsutomu , Kobayashi Tohru
Published: July 2006

A facile cyanation of acetals with trimethylsilyl cyanide, giving the corresponding α-alkoxyalkanenitriles, is achieved by using an electrogenerated acid as an acid-catalyst.
EVIDENCE OF THE SINGLET RADICAL PAIR PRECURSOR IN THE PHOTOLYTIC GENERATION OF 1,4-DIMETHYLPYRIDINYL RADICAL FROM ITS DIMER. A CIDEP STUDY
Authors: Akiyama Kimio , Tero-Kubota Shozo , Ikenoue Tsuneo , Ikegami Yusaku
Published: July 2006

Time-resolved ESR spectra of the 1,4-dimethylpyridinyl radical were observed after the photolysis of its dimer with a N2 laser. Since the transient ESR spectra exhibited the A/E polarization, singlet radical pair is proposed as the precursor of the present radical on the basis of simple sign rule.
5H-BENZO[b]THIEPINIUM AND 3H-BENZO[b]THIEPINIUM IONS
Authors: Yamazaki Shoko , Okada Koichi , Yamamoto Kagetoshi , Murata Ichiro
Published: July 2006

Both 5H-benzo[b]thiepinium and 3H-benzo[b]thiepinium ions were generated in strong acidic media and characterized by 1H- and 13C-NMR spectra: the former ion can be regarded as benzohomothiopyrylium ion whereas the latter is postulated to have localized sulfonium ion structure.
REDUCTION OF α, β-UNSATURATED CARBONYL COMPOUNDS BY A MODEL OF NAD(P)H WITH CHLOROTRIS(TRIPHENYLPHOSPHINE)RHODIUM
Authors: Nakamura Kaoru , Fujii Masayuki , Ohno Atsuyoshi , Oka Shinzaburo
Published: July 2006

α, β-Unsaturated carbonyl compounds are reduced to the corresponding saturated carbonyl compounds by a model of NAD(P)H with the aid of a rhodium(I) catalyst.
THE APPLICATION OF PHOTO-REDUCTION OF THIN CUPROUS IODIDE FILM FOR METAL IMAGE FORMATION
Authors: Shimidzu Naoki , Masuda Hideki , Ohno Shin
Published: July 2006

The surface chemical properties of cuprous-iodide (CuI) film evaporated on a polymer layer containing a precursor reducing agent, 2-isopropoxy-1,4-naphthoquinone (IPNQ), were markedly affected by UV irradiation. The CuI was reduced by photoproducts of the IPNQ and the surface reductants attracted the zinc vapor in a vacuum evaporation vessel. Thus the UV exposure resulted in the zinc vapor deposition.
CONDUCTION ELECTRON SPIN RESONANCE OF ULTRAFINE PARTICLES OF MAGNESIUM
Authors: Kimura Keisaku , Sako Sanshiro
Published: July 2006

Two resonance lines were observed in the conduction electron spin resonance of ultrafine particles of magnesium prepared in tetrahydrofuran. From the microwave frequency and the power dependencies of the resonance lines, it was found that the broader line was attributed to the quantum size effect which appears only in small particles, whereas the narrower line was due to a surface impurity.
TWO-DIMENSIONAL CHARACTER OF CRYSTAL STRUCTURE OF ORGANIC CONDUCTOR, (BMDT-TTF)3PF6(1,2-DICHLOROETHANE)
Authors: Kato Reizo , Kobayashi Akiko , Sasaki Yukiyoshi , Kobayashi Hayao
Published: July 2006

In the crystal of (BMDT-TTF)3PF6(1,2-dichloroethane) (BMDT-TTF= bis(methylenedithio)-tetrathiafulvalene), there are two crystallographically independent BMDT-TTF molecules whose molecular planes are approximately perpendicular to each other. This new type of molecular arrangement achieves the two-dimensional S···S network.
HOST-GUEST-TYPE ACID CATALYSTS DERIVED FROM CALIX[6]ARENE
Authors: Shinkai Seiji , Koreishi Hiroshi , Mori Seiichi , Sone Takaaki , Manabe Osamu
Published: July 2006

Water-soluble calix[6]arenes bearing both acidic protons and sulfonate groups were synthesized. They catalyzed a hydration reaction of 1-benzyl-1,4-dihydronicotinamide (BNAH) according to Michaelis-Menten kineticts and the rate constants were greater by 426–1220 fold than those for noncyclic analogues. Fluorescence data supported the complexation of BNAH with these water-soluble calixarenes. These findings indicate that calixarenes serve as a new starting material to design functionalized host molecules.
ORGANIC SUPERCONDUCTOR β-(BEDT-TTF)2IBr2 OBTAINED BY DIFFUSION METHOD
Authors: Saito Gunzi , Sugano Tadashi , Yamochi Hideki , Kinoshita Minoru , Oshima Kokichi , Suzuki Mitsuru , Katayama Chuji , Tanaka Jiro
Published: July 2006

It was found that an organic superconductor can be synthesized not only by electrocrystallization method but also by diffusion method between BEDT-TTF and n-Bu4N·IBr2. The superconducting phase β-(BEDT-TTF)2IBr2 shows the critical temperature of the superconducting transition at 2.0–2.3 K.
STANNOUS TRIFLATE MEDIATED ALDOL REACTION OF 3-(3-ALKOXY AND 3-AMINOPROPANOYL) THIAZOLIDINE-2-THIONES STEREOSELECTIVE SYNTHESIS OF β-LACTAM DERIVATIVES
Authors: Iwasawa Nobuharu , Huang Huamin , Mukaiyama Teruaki
Published: July 2006

The tin(II) enolate is generated from 3-acylthiazolidine-2-thione with β-alkoxy or β-amino functionality on treatment with stannous triflate in the presence of N-ethylpiperidine. The enolate further reacts with aldehyde to afford the aldol product with high syn-stereoselectivity. The aldol product thus produced is stereospecifically converted to β-lactam derivative with hydroxyethyl side chain.
PHOTOCATALYTIC FORMATION OF SCHIFF BASES FROM PRIMARY AMINES BY PLATINIZED-TiO2 SUSPENSION IN ACETONITRILE
Authors: Ohtani Bunsho , Osaki Haruyoshi , Nishimoto Sei-ichi , Kagiya Tsutomu
Published: July 2006

Photoirradiation (λex>300 nm) of platinized TiO2 suspended in Ar-purged acetonitrile solution of aliphatic and aromatic primary amines produced Schiff bases together with H2 and NH3 at room temperature. Solvent acetonitrile was partly reduced on the Pt site to inhibit the reduction of the Schiff bases into secondary amines.
HEAVY METAL ION SENSORS PREPARED FROM QUINONOID POLYMER ELECTRODES MODIFIED WITH MERCAPTIDES
Authors: Arai Gorou , Fujii Akira , Yasumori Iwao
Published: July 2006

Quinonoid polymer electrode, prepared by the electrochemical oxidation of mercaptohydroquinone, was modified with mercaptide of heavy metal ions of interest, such as Ag+ ion, Hg2+, ion, Cd2+ ion, Cu2+ ion, and Pb2+ ion. The quinonoid polymer electrodes modified with mercaptides showed a function as selective ion sensors for heavy metal ions in solution.
DISCHARGE PROPERTIES OF Mo6S8.0 AND CuY Mo6S7.75 (y=1.05 AND 2.0) IN LITHIUM SECONDARY CELLS
Authors: Uchida Takashi , Watanabe Kazuo , Wakihara Masataka , Taniguchi Masao
Published: July 2006

The discharge properties of stoichiometric Mo6S8.0, a mixture of Mo6S7.75 and Cu2.0Mo6S7.75 having the chemical formula on average of Cu1.05Mo6S7.75, and Cu2.0Mo6S7.75 in lithium secondary cells were examined in the first cycle. When stoichiometric Mo6S8.0 was discharged at a current density of 0.5 mA cm−2, as much as 3.9 lithium ions per formula unit of Mo6S8.0 were incorporated at a cut-off voltage down to 1 V.
NEIGHBORING GROUP PARTICIPATION IN CARBENE CHEMISTRY. EFFECT OF NEIGHBORING CARBOXYLATE GROUP ON ARYLCARBENE REACTIVITY
Authors: Tomioka Hideo , Tabayashi Kazuo , Izawa Yasuji
Published: July 2006

The carbene generated by photolysis of sodium α-diazoacetate in a binary mixture of methanol and 2-methyl-2-butene showed 3 000 times enhanced reactivity toward methanol relative to the alkene compared to that derived from the corresponding ester or acid. The results are interpreted as indicating that the neighboring carboxylate group interacts with electron-deficient center of carbene.
MICHAEL REACTION OF 1,2-CYCLOHEXANEDIONES AND 1,2-CYCLOPENTANEDIONES WITH METHYL VINYL KETONE
Authors: Utaka Masanori , Fujii Yasuyuki , Takeda Akira
Published: July 2006

The Michael reaction of 1,2-cyclohexanediones with methyl vinyl ketone is highly dependent upon the structure of dione or the catalyst, base or ZnCl2, affording 3-(3-oxobutyl)-2-hydroxy-2-cyclohexen-1-one or 1-hydroxy-7-acetylbicyclo[3.2.1]octan-8-one as major products. 1,2-Cyclopentanediones react with methyl vinyl ketone somewhat differently.
SYNTHESIS OF PHENOLS BY POLYKETIDE CONDENSATION AND AN EFFICIENT SYNTHESIS OF 3,5-DIOXOALKANOATES FROM AMIDES
Authors: Yamaguchi Masahiko , Shibato Keisuke , Hirao Ichiro
Published: July 2006

Several phenols were synthesized from dimethyl β,β′,δ,δ′-tetraoxoalkanedioates, which were prepared by the condensation of methyl acetoacetate dianion with N,N,N′,N′-tetramethylalkanediamides in the presence of BF3·OEt2.
THE REDUCTIVE LITHIATION OF THIOACETALS, α,α-BIS(TRIMETHYLSILYL)ALKYL SULFIDES, AND 2-ALKYL-2-ETHYLTHIOALKANENITRILES USING TRIBUTYLSTANNYLLITHIUM
Authors: Takeda Takeshi , Ando Kazuo , Mamada Akira , Fujiwara Tooru
Published: July 2006

The reaction of thioacetals of phenyl ketones, α,α-bis(trimethylsilyl)alkyl sulfides, and 2-alkyl-2-ethylthioalkanenitriles with tributylstannyllithium gave the corresponding α-anions of sulfides, α,α-bis(trimethylsilyl)alkane, and nitriles, respectively.
A NEW CLAISEN APPROACH TO THE STEREOSPECIFIC INTRODUCTION OF A STEROID SIDE CHAIN AT C-20. A SIMPLE SYNTHESIS OF 20-EPICHOLESTEROL VIA THE β-FACE REARRANGEMENT
Authors: Mikami Koichi , Kawamoto Kazuya , Nakai Takeshi
Published: July 2006

A simple synthesis of 20-epicholesterol is described which relies on the unprecedented β-face Claisen rearrangement of an E−Δ17(20)-16β-vinyloxy steroid leading exclusively to the “unnatural” 20S chirality.
NON-DISSOCIATIVE LIGAND CONTROL OVER THE REDUCTIVE ELIMINATION OF η3-ALLYL COMPLEXES OF Pd(II)
Authors: Kurosawa Hideo , Emoto Mitsuhiro
Published: July 2006

Kinetic studies on reductive elimination of η3-allyl(aryl)–palladium(II) complexes suggest lack of ligand dissociation prior to the C–C coupling. On the contrary, the fourth ligand which remains coordinated plays an important role, by virtue of its electronic effect, in determining the barrier to the C–C coupling.
DIELECTRIC BEHAVIOR OF 2-METHYL-2-PROPANOL AND BUTANOL ISOMERS IN SOLUTIONS
Authors: Sato Hiroshi , Nakamura Haruki , Itoh Koichi , Higasi Keniti
Published: July 2006

The principal relaxation times of four isomeric butanols were measured at 25 °C in cyclohexane solutions by the TDR method and compared with those obtained in solutions of benzene and pyridine. The dielectric behavior of 2-methyl-2-propanol is found to be vastly different from other butanols.
INTERMEDIACY OF 1,2,4,5-DIOXADITHIANES IN THE CONVERSION OF THIOBENZOPHENONES INTO BENZOPHENONES. A NEW RING SYSTEM FORMATION
Authors: Baran Janusz , Houbrechts Yvette , Laszlo Pierre
Published: July 2006

3,3,6,6-tetraaryl-1,2,4,5-dioxadithianes, containing a new heterocycle, are isolated and characterized as reaction intermediates in thiocarbonyls to carbonyls transformations using clay supported metal nitrates. We propose a plausible mechanism, explaining the nitrosating behaviour of the reagent in this process.
CONFORMATION OF CYCLO(-l-PRO-d-LEU-d-TYR(ME)-l-ILE-) PREDICTED BY EMPIRICAL RULES FOR CYCLIC TETRAPEPTIDES WAS EVIDENCED BY 1H- AND 13C-NMR SPECTROSCOPY
Authors: Kato Tetsuo , Tone Akira , Kodera Yasushi , Lee Sannamu , Shimohigashi Yasuyuki , Izumiya Nobuo
Published: July 2006

The predicted cis-trans-cis-trans backbone conformation of cyclo(-l-Pro-d-Leu-d-Tyr(Me)-l-Ile-) (2) has been evidenced by 1H-NMR experiments. Peptide 2 and cyclo(-l-Pro-l-Leu-d-Tyr(Me)-l-Ile-) are the first diaste-reomeric peptides having cis (Dd) and trans (Ld) Leu-Tyr(Me) peptide bonds.
PHOTOCHEMICAL REACTION OF N-METHYLPHENANTHRENE-9,10-DICARBOXIMIDE WITH SECONDARY AMINES. AMINOLYSIS FROM N–H ABSTRACTION
Authors: Kubo Yasuo , Egusa Chie , Araki Takeo
Published: July 2006

Photolysis of N-methylphenanthrene-9,10-dicarboximide (PI) with diethylamine (1a) in benzene gave an aminolysis product together with reduction-products and other coupling products. Effects of addition of 1-propanethiol and concentration of 1a indicate that the aminolysis appears to arise from N–H abstraction mainly by excited triplet state of PI.
ZnBr2-MEDIATED HIGHLY DIASTEREOSELECTIVE ADDITION OF GRIGNARD REAGENTS TO α-BENZYLOXY ALDEHYDES
Authors: Asami Masatoshi , Kimura Rieko
Published: July 2006

α-Benzyloxy aldehydes reacted with Grignard reagents in the presence of ZnBr2 to afford vicinal syn-diol derivatives with high diastereoselectivity.
THE SYNTHESIS OF AMIDES, ESTERS, AND THIOESTERS
Authors: Miyake Muneharu , Kirisawa Makoto , Tokutake Norio
Published: July 2006

Diethyl 2-(3-oxo-2,3-dihydro-1,2-benzisosulfonazolyl)phosphonate is a highly reactive condensing agent, which provides good yield route to amides, esters, and thioesters from a variety of amines, active hydroxylamines, and thiols and acids.
CRYSTAL STRUCTURES AND ELECTROCHEMICAL PROPERTIES OF ORGANIC DONORS, BMDT-TTF AND BEDSe-TSeF. TWO MODIFICATIONS OF BEDT-TTF
Authors: Kato Reizo , Kobayashi Hayao , Kobayashi Akiko , Sasaki Yukiyoshi
Published: July 2006

Almost planar BMDT-TTF molecules form a side-by-side one-dimensional array along the [101] direction, while BEDSe-TSeF molecules are non-planar and dimerized. Electrochemical studies reveal two oxidation waves of BMDT-TTF at potentials similar to those of BEDT-TTF, and BEDSe-TSeF shows one oxidation wave at a potential higher than the second oxidation of BEDT-TTF.
STEREOSPECIFIC PHOTODIMERIZATION OF UNSATURATED COMPOUNDS INDUCED BY NICKEL COMPLEXES
Authors: Miyashita Akira , Ikezu Shohgo , Nohira Hiroyuki
Published: July 2006

Irradiation of (ethylene)bis(triphenylphosphine)nickel (1) or bis(triphenylphosphine)nickelacyclopentane induced stereospecific cyclodimerization of substituted olefins such as acrylonitrile and methylacrylate affording trans-1,2-disubstituted cyclobutanes, while 1,7-octadiene was converted to trans-bicyclo[4.2.0]octane. Ethylene was photochemically dimerized to cyclo- and linear dimers induced by 1.
COLLOIDAL PLATINUM CATALYSTS PREPARED BY HYDROGEN- AND PHOTO-REDUCTION IN THE PRESENCE OF SURFACTANT
Authors: Toshima Naoki , Takahashi Tadahito , Hirai Hidefumi
Published: July 2006

Chloroplatinic acid in an aqueous solution was reduced by hydrogen molecules or photo-irradiation in the presence of surfactants to produce colloidal dispersions of platinum protected by the surfactants. The particles of the colloidal platinum prepared by photo-reduction were smaller in size and more narrowly dispersed than those prepared by hydrogen-reduction. They worked as highly active catalysts for hydrogenation of olefins.
THE REACTION OF β-PHENYLSULFINYL β,γ-UNSATURATED ETHERS WITH TRIBUTYLSTANNYLLITHIUM. A NEW ROUTE TO SUBSTITUTED ALLENES
Authors: Takeda Takeshi , Suzuki Koichi , Ohshima Hiroyuki , Fujiwara Tooru
Published: July 2006

Substituted allenes were prepared in good yields by the reaction of β-phenylsulfinyl β,γ,-unsaturated ethers with tributylstannyllithium.
ROLE OF URIC ACID, CYSTEINE, AND GLUTATHIONE AS CHAIN BREAKING ANTIOXIDANT IN AQUEOUS PHASE
Authors: Niki Etsuo , Yamamoto Yorihiro , Kamiya Yoshio
Published: July 2006

Uric acid, cysteine, and glutathione suppressed the oxidations of methyl linoleate, soybean phosphatidylcholine, and erythrocyte ghosts in aqueous dispersions initiated with a water-soluble azo initiator. It was suggested that these compounds might function as a chain breaking antioxidant in vivo by scavenging oxygen radicals in an aqueous phase.
CATALYTIC PROPERTIES OF THE PLATINUM AND PALLADIUM BLACKS OBTAINED FROM VAPORIZED METALS AS REVEALED IN THE HYDROGENATION OF 4-METHYLCYCLOHEXANONE IN ETHANOL
Authors: Nishimura Shigeo , Iwafune Sei-ichiro , Nagura Toshikazu , Akimoto Yoshinori , Uda Masahiro
Published: July 2006

The platinum and palladium blacks obtained from vaporized metals have been found to catalyze the acetal formation efficiently in the hydrogenation of 4-methylcyclohexanone in ethanol. The catalytic properties of these blacks are compared with those of various blacks prepared by chemical procedures.
ELECTRICALLY ACTIVATED MECHANOCHEMICAL DEVICES USING POLYELECTROLYTE GELS
Authors: Osada Yoshihito , Hasebe Mariko
Published: July 2006

We report the first model of electrically activated mechanochemical system made of polyelectrolyte gels which contracts, oscillates, and bends reversibly. On the basis of this principle a variety of devices which function under electric stimulus, i.e., a “chemical valve” membrane expanding and contracting the pore size, a switching oscillating 15 to 100 times per minute, and a composite bending like “bimetal” were developed.
THE CRYSTAL AND ELECTRONIC STRUCTURES OF BEDT-TTF2I2Br
Authors: Kobayashi Hayao , Kato Reizo , Kobayashi Akiko , Saito Gunzi , Tokumoto Madoka , Anzai Hiroyuki , Ishiguro Takehiko
Published: July 2006

The crystal structure of BEDT-TTF2I2Br is isomorphous to the well-known superconductor, β-BEDT-TTF2I3. The suppression of the superconductivity in BEDT-TTF2I2Br down to at least 0.5 K, will be ascribed to the orientational disorder of the I2Br anions. Examination of the intermolecular overlap integrals indicates that the system has a two-dimensional closed Fermi surface.
SELECTIVE SYNTHESIS OF C2-OXYGENATES BY CO HYDROGENATION OVER SILICA-SUPPORTED Co–Ir CATALYST
Authors: Kintaichi Yoshiaki , Kuwahara Yasushi , Hamada Hideaki , Ito Takehiko , Wakabayashi Katsuhiko
Published: July 2006

Silica-supported Co–Ir bimetallic catalyst was effective for the selective synthesis of C2-oxygenates such as ethanol, acetaldehyde, and acetic acid by vapor-phase CO hydrogenation at 280–320 °C and 51 atm. It is suggested that Co–Ir catalyst may form an active species responsible for the synthesis of C2-oxygenates.
THE ENHANCED FORMATION OF C2-OXYGENATES IN THE HYDROGENATION OF CARBON MONOXIDE OVER THE MODIFIED COBALT CATALYSTS
Authors: Sugi Yoshihiro , Takeuchi Kazuhiko , Matsuzaki Takehiko , Arakawa Hironori
Published: July 2006

The formation of C2-oxygenates was enhanced by the modification of Co/SiO2 catalyst, prepared from cobalt(II) acetate, with transition metal (Ru or Re) and alkaline earth in the hydrogenation of carbon monoxide. The X-ray photoelectron spectra suggest that the cobalt is kept in the moderate oxidation state by synergetic effects of transition metal and alkaline earth. The formation of C2–O occurrs on the partly reduced cobalt site.
CATALYTIC OXIDATION OF THIOLS BY COENZYME PQQ
Authors: Itoh Shinobu , Kato Nobuyuki , Ohshiro Yoshiki , Agawa Toshio
Published: July 2006

Oxidation of thiols by coenzyme PQQ as a new enzymatic oxidation-reduction model was found to proceed catalytically under aerobic conditions to give corresponding disulfides.
C–C BOND FORMATION BY THE PHOTOINDUCED REACTIONS OF cis-DIALKYLCOBALT(III) COMPLEXES WITH BENZYL AND ALLYL BROMIDES
Authors: Fukuzumi Shunichi , Ishikawa Kunio , Tanaka Toshio
Published: July 2006

The photocleavage of cobalt-carbon bonds of cis-dialkylcobalt(III) complexes, cis-[R2Co(bpy)2]ClO4 (R = Me, Et, and PhCH2; bpy = 2,2′-bipyridine), induces the selective C–C bond formation from benzyl and allyl bromides to yield 1,2-diphenylethane and 1,5-hexadiene, respectively. The monoalkylcobalt(II) complexes [RCo(bpy)2]+ formed by the photocleavage reactions are responsible for the selective reduction of benzyl and allyl bromides.
ASYMMETRIC REDUCTION OF PROCHIRAL HYDROXY KETONES WITH A CHIRAL REDUCING AGENT PREPARED FROM TIN(II) CHLORIDE, A CHIRAL DIAMINE, AND DIISOBUTYLALUMINUM HYDRIDE
Authors: Mukaiyama Teruaki , Tomimori Koji , Oriyama Takeshi
Published: July 2006

Asymmetric reduction of prochiral α- and β-hydroxy ketones with a reagent, generated from tin(II) chloride, a chiral diamine, and diisobutylaluminum hydride, afforded the corresponding dihydroxy compounds in good chemical and optical yields. Optical yields depended on the nature of the protective groups of hydroxyl function.
DIELECTRIC RELAXATION OF 1-PROPANOL IN 1,4-DIOXANE AND CYCLOHEXANE
Authors: Yagihara Shin , Nozaki Ryusuke , Mashimo Satoru , Higasi Ken-iti
Published: July 2006

Dielectric relaxation times of 1-propanol were measured in 1,4-dioxane and cyclohexane at 25 °C by the TDR method. Dielectric behavior of this alcohol varied greatly according to the nature of the solvent. A single relaxation process was observed when the hydrogen bonding solvent was employed, while two separate relaxation processes were found in the inert solvent.
SPECTROPHOTOMETRIC DETERMINATION OF PARTS PER BILLION LEVEL PHOSPHATE BY “STOPPED-FLOW TIME DIFFERENCE ANALYSIS” USING MALACHITE GREEN AND MOLYBDATE
Authors: Kanaya Ken-ichiro , Hiromi Keitaro
Published: July 2006

The “stopped-flow time difference analysis” method [K. Hiromi, C. Kuwamoto, and M. Ohnishi, Anal. Biochem., 101, 421 (1980)] was applied to the rapid and simple determination of trace amounts of phosphate, using Malachite Green and molybdate. The specific determination of phosphate down to the ppb level was successfully carried out even in the presence of 20 fold-excess (w/w) of AsO43−. The detection limit was as low as 2 ppb.
HYDROSILYLATION OF 1,4-BIS(TRIMETHYLSILYL)-1,3-BUTADIYNE
Authors: Kusumoto Tetsuo , Hiyama Tamejiro
Published: July 2006

Hydrosilylation of 1,4-bis(trimethylsily)-1,3-butadiyne with platinum and rhodium catalyst proceeded stepwise to give first 2-silyl-1,4-bis(trimethylsilyl)-1-buten-3-ynes and then 1,3-disilyl-1,4-bis(trimethylsilyl)-1,2-butadienes in high yields.
N-PROTONATED AZOMETHINE YLIDES WITH A LEAVING GROUP AS SYNTHETIC EQUIVALENTS FOR NONSTABILIZED NITRILE YLIDES
Authors: Tsuge Otohiko , Kanemasa Shuji , Matsuda Koyo
Published: July 2006

Through alkylation or silylation and then desilylation steps, N-(silylmethyl)amidines generate N-protonated azomethine ylides which cycloadd to olefins, acetylenes, and aldehydes giving 1- or 2-pyrrolines, pyrroles, and 2-oxazolines, respectively, after the elimination of N-substituted anilines. With this sequence, the amidines are useful synthetic equivalents of nonstabilized nitrile ylides.
REACTION OF HYDROXIDE ION WITH ELECTRON ACCEPTORS IN ACETONITRILE
Authors: Umemoto Kisaburo
Published: July 2006

The reaction of hydroxide ion with electron acceptors gave reaction products identical to those obtained by the reaction of these electron acceptors with electron donors. The results indicate that hydroxide ion works as a reductant in acetonitrile.
PRELIMINARY TREATMENT WITH AMMONIA IN REDUCTION OF CuY ZEOLITE
Authors: Tanabe Shuji , Matsumoto Hiroshige
Published: July 2006

The reduction process of CuY zeolite has been investigated in temperature programmed experiments. The reduction of Cu2+ ions with H2 occurred by a two-step mechanism, via Cu+ ions to Cu metal. In the first step of reduction NH3 was used as the reducing agent instead of H2. Copper particles in the reduced zeolite with the NH3-pretreatment were uniformly dispersed compared to those without the NH3-pretreatment. The average diameters of the particles were estimated to be 8.4 nm for the former and 18.5 nm for the latter.
REGIO- AND DIASTEREOSELECTIVE ALDOL REACTION OF 1,2-CYCLOHEXANEDIONE DIANIONS WITH ALDEHYDES
Authors: Utaka Masanori , Hojo Makoto , Takeda Akira
Published: July 2006

The aldol reaction of 1,2-cyclohexanedione dianions with various aldehydes afforded threo and erythro aldols in a ratio of 82:18−>99:1 in 60–85% yields. A diastereoselective synthesis of racemic corynomycolic acid was achieved by using the reaction.
RHODIUM-CATALYZED AZACARBONYLATION OF ALLYL PHOSPHATES. THE PREPARATION OF β,γ-UNSATURATED AMIDES FROM ALLYL ALCOHOLS
Authors: Murahashi Shun-Ichi , Imada Yasushi
Published: July 2006

Allyl phosphates undergo a smooth azacarbonylation reaction with amines to afford β,γ-unsaturated amides at 50 °C under CO atmosphere (20 atm) in the presence of Rh6(CO)16 catalyst and Bu4NCl co-catalyst.
SELECTIVE ETHYLENE ADSORBENTS COMPOSED OF COPPER(I) CHLORIDE AND POLYSTYRENE RESINS HAVING AMINO GROUPS
Authors: Hirai Hidefumi , Kurima Kazunori , Wada Keiichiro , Komiyama Makoto
Published: July 2006

A selective adsorbent for ethylene is prepared by stirring 15 g of copper (I) chloride and 10 g of polystyrene resin having primary and secondary amino groups in 1:1 (v/v) acetonitrile–water mixture, followed by removal of the liquid phase. The adsorbent adsorbs 15.0 mmol of ethylene at 20 °C, 1 atm, which is 7.9 fold larger than the value (1.9 mmol) for ethane.
CYCLODEXTRIN-CATALYZED HYDROLYSIS OF ESTERS BEARING A HYDROPHOBIC TAIL
Authors: Ueno Akihiko , Suzuki Iwao , Hino Yoshihiro , Suzuki Atsuko , Osa Tetsuo
Published: July 2006

γ-Cyclodextrin-catalyzed hydrolysis of p-nitrophenyl esters bearing a long alkyl chain proceeded with larger rate acceleration than those with a short alkyl chain. Such rate acceleration behavior was not observed with β-cyclodextrin. The results suggest that the esters with a long alkyl chain take a folded structure (Type A) in the γ-cyclodextrin cavity.
CYCLOADDITIONS OF N-BENZYLIDENEAMINOACETONITRILE AS A SYNTHETIC EQUIVALENT OF METHANENITRILE BENZYLIDE
Authors: Tsuge Otohiko , Kanemasa Shuji , Yorozu Kiyotaka , Ueno Kazunori
Published: July 2006

N-Benzylideneaminoacetonitrile is a synthetic equivalent of methanenitrile benzylide via a cycloaddition and elimination sequence. Its reactions with olefinic dipolarophiles provide stereochemically defined 1- or 2-pyrrolines.
GENERATION OF ARENEDIAZONIUM ION FROM MOLECULAR COMPLEX OF α-AZOHYDROPEROXIDE WITH SOLVENTS. A NEW ROUTE FOR DIAZONIUM ION
Authors: Tezuka Takahiro , Ando Setsuo
Published: July 2006

Arenediazonium ions are generated from molecular complexes of α-azohydroperoxides with solvents (crystals or oils) under anhydrous conditions, when the solvated molecules are removed from these complexes.
SORPTION OF NICKEL ON CERIUM(IV)-BASED ION-EXCHANGERS
Authors: Nyamah David
Published: July 2006

Sorption of nickel on the oxide, phosphate, antimonate, and tungstate of cerium has been studied at pH 4.0 as a function of nickel ion concentration. The absorption on cerium tungstate and hydrous cerium oxide was linearly related to the nickel ion concentration up to 0.08 M.
FIRST REPORT OF THE REDUCTIVE NITROSYLATION OF TUNGSTATE(VI) BY HYDROXYLAMINE. STEREOSPECIFIC SYNTHESIS OF [w(NO)2Cl2(L)2] (L = py, 3-Mepy, 4-Mepy)
Authors: Sarkar Sabyasachi , Mohammad Ishaq B , Subramanian Periyasamy
Published: July 2006

Stereospecific synthesis of cis-dichlorotrans-bis(pyridine)-cis-dinitrosyltungsten(O) and the related 3-picoline and 4-picoline derivatives have been achieved by a single pot reductive nitrosylation of sodium tungstate(VI) by hydroxylamine in the presence of excess of pyridine (or picolines) as solvent.
APPLICATION OF THE METHOD OF CONTINUOUS VARIATION TO A SOLID–LIQUID REACTION
Authors: Hihara Goro , Miyamae Hiroshi , Nagata Miharu
Published: July 2006

A method has been developed for the identification of all the insoluble complexes formed in a solid-liquid reaction of an insoluble Lewis acid with a soluble Lewis base by extending the method of continuous variation to such a heterogeneous system. It was applied to the reaction of PbI2 with pyridine(py) in ethanol solution. Two insoluble complexes, PbI2·py and PbI2·2py, were identified.
MESOIONIC THIOCARBONYL YLIDES
Authors: Araki Shuki , Butsugan Yasuo
Published: July 2006

Four kinds of mesoionic thiocarbonyl ylides were synthesized by the treatment of mesoionic thiolate with bromine followed by the reaction with conjugate base of active methylene compounds. The structures were discussed based on the spectroscopic properties.
OXIDATION OF UNACTIVATED CARBON ATOMS OF LUPANE AND FRIEDELANE-TYPE TRITERPENES WITH m-CHLOROPERBENZOIC ACID
Authors: Tori Motoo , Matusuda Reiko , Asakawa Yoshinori
Published: July 2006

The reaction of lupan-3β,28-diyl diacetate, lupan-3β-yl acetate, and friedelan-3β-yl acetate with m-chloroperbenzoic acid gave their hydroxy or keto derivatives upon oxidation of unactivated carbon atoms.
REDUCTION OF AROMATIC NITRO COMPOUNDS WITH SODIUM TELLURIDE
Authors: Suzuki Hitomi , Manabe Hajime , Inouye Masahiko
Published: July 2006

Sodium telluride, prepared by heating tellurium with Rongalite in aqueous sodium hydroxide, easily reduces aromatic nitro compounds to the corresponding amines in good yields. The reduction can be carried out using a catalytic amount of tellurium, since sodium telluride is readily regenerated in the presence of excess Rongalite.
PHOTOCHEMICAL REACTION OF 2-ALKENOYL-3-ALKOXY-1,4-BENZOQUINONES. FORMATION OF 5H-PYRANO[4,3,2-de][1,3] BENZODIOXIN DERIVATIVES
Authors: Maruyama Kazuhiro , Iwamoto Hidetoshi , Soga Osamu , Takuwa Akio , Osuka Atsuhiro
Published: July 2006

A number of 3-alkoxy-5-methyl-2-(α-methylcinnamoyl)-1,4-benzoquinones have been prepared by the reaction of 5-methyl-2-(α-methylcinnamoyl)-1,4-benzoquinone with alcohols. Irradiation of 3-methoxy-, 3-ethoxy-, and 3-isopropoxy-5-methyl-2-(α-methylcinnamoyl)-1,4-benzoquinones in solution gave 5H-pyrano[4,3,2-de][1,3]benzodioxins.
A SIMPLE STEREOCONTROLLED SYNTHESES OF OPTICALLY ACTIVE DEOXYSUGARS l-RHODINOSE AND d-AMICETOSE
Authors: Itoh Toshiyuki , Yoshinaka Atsuya , Sato Toshio , Fujisawa Tamotsu
Published: July 2006

Facile stereoselective syntheses of 2,3,6-trideoxysugars, l-rhodinose and d-amicetose, were achieved from highly diastereoselective nucleophilic addition of methyl group to (S)-2-benzyloxy-5-hexenal, which was easily obtained from optically pure (S)-glycidyl sulfide.
ELECTROCHEMICAL BEHAVIORS OF CYCLOPOLYSILANES. OXIDATION POTENTIALS VIA CYCLIC VOLTAMMETRY
Authors: Watanabe Hamao , Yoshizumi Koichi , Muraoka Tsutomu , Kato Motohiko , Nagai Yoichiro , Sato Takeo
Published: July 2006

The anodic peak potentials for a series of cyclopolysilanes, [R1R2Si]n (n=3–7), lowered with decreasing ring size and were found to be parallel to the lowest transition energies determined by the UV absorptions. In the anodic oxidation these cyclopolysilanes undergo the initial one electron transfer reaction to give a cation radical which leads to the formation of an acyclic α,ω-radical cation followed by the second electron transfer to give the corresponding di-cation.
TOTAL SYNTHESIS OF (±)-(Z)-9-(BROMOMETHYLENE)-1,5,5-TRIMETHYLSPIRO[5.5]UNDECA-1,7-DIEN-3-ONE, A BROMINATED SESQUITERPENE OF CHAMIGRANE TYPE
Authors: Niwa Haruki , Yoshida Yoshifumi , Hasegawa Takashi , Yamada Kiyoyuki
Published: July 2006

The first total synthesis of (±)-(Z)-9-(bromomethylene)-1,5,5-trimethylspiro[5.5]undeca-1,7-dien-3-one, a chamigrane sesquiterpene having a novel bromomethylene group is described.
ORGANOALUMINUM-INDUCED ADDITION OF POLYHALOMETHANE TO OLEFINS
Authors: Maruoka Keiji , Sano Hiromi , Fukutani Yoshimi , Yamamoto Hisashi
Published: July 2006

A mild procedure for the trimethylaluminum-induced addition of polyhalomethane to olefins has been described.
HALOGEN-EXCHANGE FLUORINATION OF CYCLO AND TERTIARY ALKYL HALIDES USING Cu2O-HF-ORGANIC BASE SOLUTIONS
Authors: Yoneda Norihiko , Fukuhara Tsuyoshi , Nagata Seiji , Suzuki Akira
Published: July 2006

Cu2-O-HF-Organic base (tetrahydrofuran or Et2-O) solutions were used successively as a highly reactive halogen-exchange fluorination reagent for the cyclo or tertiary alkyl halides without carbon skeletal rearrangement under the mild conditions.
APPLICATION OF [2,3]WITTIG REARRANGEMENT IN STEROID SIDE CHAIN SYNTHESIS. A NEW ENTRY TO (22R)-HYDROXY-23-ACETYLENIC SIDE CHAINS VIA THE β-FACE REARRANGEMENT
Authors: Mikami Koichi , Kawamoto Kazuya , Nakai Takeshi
Published: July 2006

A new entry to (22R)-hydroxy-23-acetylenic steroid side chains is described which relies on the concept of chirality transfer via the unprecedented β-face [2,3]Wittig process. The key feature is that the C-16β chirality is completely transmitted to the two new chiral centers at C-20 and C-22 with a high erythro-selectivity.
APPLICATION OF ASYMMETRIC [2,3]WITTIG REARRANGEMENT TO STEREOCONTROL OVER THREE CONTIGUOUS CHIRAL CENTERS. A NEW SYNTHESIS OF (+)-BLASTMYCINONE
Authors: Sayo Noboru , Nakai Ei-ichi , Nakai Takeshi
Published: July 2006

A new synthesis of (+)-blastmycinone is described which relies on the combination of the asymmetric [2,3]Wittig rearrangement with the selective reduction of an α-hydroxy ketone with zinc borohydride.
ASYMMETRIC [2,3]WITTIG SIGMATROPIC REARRANGEMENTS INVOLVING CHIRAL AMIDE ENOLATES AS THE MIGRATING TERMINI
Authors: Mikami Koichi , Takahashi Osamu , Kasuga Takashi , Nakai Takeshi
Published: July 2006

The title rearrangement of the chiral (E-crotyloxy)acetamides derived from (S)-prolinol has been shown to provide a modest level of asymmetric induction (52–60%) along with a high erythro-selectivity (95–98%). The influence of the metal centers (Li, K, and Zr) and the ligating substituents on the prolinol part has been discussed.
AN INTRAMOLECULAR FRIEDEL-CRAFTS ACYLATION OF ROTAMERIC 9-(2-CARBOXY-1,1-DIMETHYLETHYL)-1,4-DIMETHYLTRIPTYCENE
Authors: Yonemoto Katsumi , Nakai Yasufumi , Yamamoto Gaku , Oki Michinori
Published: July 2006

While the ap form of the title compound, on being heated with thionyl chloride, afforded 3-oxo-1,1,8,11-tetramethyl-2,3,7,11b-tetrahydro-7,11b-o-benzenobenzo[j]phenalene and 3-chloro-1,1,8,11-tetramethyl-7,11b-dihydro-7,11b-o-benzenobenzo[j]phenalene, the sc-isomer did, in addition to the above products, those derived from the ipso attack of the intervening acyl cation on the 1-position, the methyl group at the position undergoing the 1,2-shift.
OXYGEN PERMEATION THROUGH PEROVSKITE-TYPE OXIDES
Authors: Teraoka Yasutake , Zhang Hua-Min , Furukawa Shoichi , Yamazoe Noboru
Published: July 2006

The rate of oxygen permeation through La1−xSrxCo1−yFeyO3−δ was found to increase with an increase in Sr or Co content, showing that the permeability was mainly controlled by the amount of oxygen vacancies. The results obtained indicate that mixed conductive perovskite-type oxides are promising materials for oxygen permeation at elevated temperatures.