bluuebunny/crossref_metadata_2025 huggingface dataset:
Kinetics and Mechanism of the Reduction of Dodecatungstocobaltate(III) by Iminodiacetate, Nitrilotriacetate, and Ethylenediaminetetraacetate. A Comparative Study of the Reactivity of Different Amine-N-carboxylates
Authors: K. Saha Swapan , Bhattacharya Prabir , Ali Mahammad , Banerjee Pradyot
Published: July 2006

The kinetics of reduction of dodecatungstocobaltate(III) by iminodiacetate (IDA), nitrilotriacetate (NTA), and ethylenediaminetetraacetate (EDTA) have been studied in aqueous solution at 50 °C, 30 °C, and 15 °C respectively. In general, the reactivity of the amine-N-carboxylates is in the order EDTA>NTA>IDA. All the anionic species have been found to undergo oxidation via both a spontaneous and an alkali metal ion-catalyzed pathway, while molecular form of the acids are oxidized only via spontaneous pathway. The rate of oxidation is given by a general expression kox=k°+k[M+]n where kox=kobs/2[L]T([L]T=total concentration of a particular amine-N-carboxylate) and n may have values 1 or 2 depending on the nature of M+. The terms k° and k account for the rate constants of the spontaneous and catalyzed paths respectively. A general trend K+>Na+>Li+ for the catalyzed path has been observed for the oxidation of these amine-N-carboxylates. Reactivities of different species present in the experimental pH range have been evaluated by carrying out experiment at different pH and using these data in appropriate rate expressions. The reactivities (50 °C) of Hida− are k°=4.70×10−5 dm3 mol−1 s−1 and k1=3.44×10−4 dm6 mol−2 s−1 for the spontaneous and Na+ catalyzed paths respectively. For NTA oxidation (30 °C), rates are k10°(H3nta)=1.11×10−3 dm3 mol−1 s−1, k11°(H2nta−, spontaneous)=7.00×10−3 dm3 mol−1 s−1, k11(H2nta−, Na+ catalyzed)=3.50×10−2 dm6 mol−2 s−1, k12°(Hnta2−, spontaneous)=7.20×10−3 dm3 mol−1 s−1, k12(Hnta2−, Na+ catalyzed)=4.01×10−2 dm6 mol−2 s−1. The corresponding reactivities (15 °C) for EDTA oxidation are k20°(H4edta, spontaneous)=6.80×10−3 dm3 mol−1 s−1, k21°(H3edta−, spontaneous)=4.80×10−2 dm3 mol−1 s−1, k21(H3edta−, Na+ catalyzed)=0.48 dm9 mol−3 s−1, k22°(H2edta2−, spontaneous)=0.21 dm3 mol−1 s−1, k22(H2edta2−, Na+ catalyzed)=1.70 dm6 mol−2 s−1, k23°(Hedta3−, spontaneous)=1.71 dm3 mol−1 s−1, k23(Hedta3−, Na+ catalyzed)=30.00 dm6 mol−2 s−1. A plausible mechanism considering an outersphere association between the complex and reductant has been suggested where the alkali metal ions are assumed to act as a bridge between the reactants.
Stopped-Flow Kinetic Investigations of One-Electron Transfer Reactions of Phenothiazines and Their Radical Cations in Aqueous Solution
Authors: Venkatasubramanian Lakshmanan , Maruthamuthu Pichai
Published: July 2006

The kinetics of one-electron oxidation of the protonated forms of phenothiazines namely, chlorpromazine (CPZH+) and promethazine (PMZH+) with the inorganic peroxides, peroxomonosulfate and peroxodisulfate in aqueous medium, were investigated by stopped flow spectrophotometric technique. The reactions of both the phenothiazines obeyed a total second-order kinetics, first-order each with respect to [phenothiazine] and [peroxide]. Both peroxides generated radical cations from the respective phenothiazines by one-electron transfer. The radical cations, CPZH·2+ and PMZH·2+ were found to oxidize ascorbic acid generating the parent compounds, whereas CPZH·2+ alone was able to react with sulfite, thiosulfate and dithionite to regenerate CPZH+. The kinetics of all these reactions were investigated and discussed.
Convenient Synthesis of Cyclic Trithiocarbonates from 1,2- or 1,3-Dihaloalkanes and Sodium Trithiocarbonate in the Presence of Phase-Transfer Catalyst
Authors: Sugawara Akira , Sato Tsukasa , Sato Ryu
Published: July 2006

Cyclic trithiocarbonates, such as 1,3-dithiolane-2-thiones and 1,3-dithiane-2-thiones, were conveniently synthesized by treating 1,2- or 1,3-dihaloalkanes with sodium trithiocarbonate in the presence of a phase-transfer catalyst.
Selective Formation of Ethene from CO Hydrogenation Reaction over In2O3–CeO2, –La2O3, and –Y2O3 Mixed Oxide Catalysts
Authors: Arai Toru , Maruya Ken-ich , Domen Kazunari , Onishi Takaharu
Published: July 2006

CO hydrogenation over mixed oxides of 3A and 4A Groups (Y2O3, La2O3, CeO2, and ZrO2) with 3B Group (Al2O3, Ga2O3, and In2O3) was carried out. The addition of Ga2O3 or In2O3 to Y2O3, La2O3, and CeO2 enhances the formation of light alkenes. An In2O3–CeO2 catalyst shows the highest selectivity (43%) for ethene with the lowest selectivity (0.5%) for ethane in total hydrocarbons produced. The addition of In2O3 to CeO2 results in an increase in activity for the CO hydrogenation reaction. From the results of an ethene hydrogenation reaction over mixed oxide catalysts, the high selectivity for alkene formation over In2O3-containing catalysts is due to a suppression of alkene hydrogenation by the addition of In2O3. Indium in CeO2 is highly dispersed while keeping an oxidation state of +1 or +3 under the reaction conditions.
Effects of Solvent and Temperature on the 1,4-Asymmetric Induction in the Diastereoselective Hydrogenation of Dehydrodipeptides
Authors: Ikeda Satoru , Yamagishi Takamichi , Yamaguchi Motowo , Hida Mitsuhiko
Published: July 2006

A study of the effets of solvent and temperature on the stereoselectivity of asymmetric hydrogenation of dehydrodipeptides has been made with Rh(I)–(DPP-AE) catalyst, in which an electrostatic interaction is possible between the dimethylamino group of the ligand and the carboxyl group of the substrate. The highest stereoselectivity was attained in the MeOH–water solvent, while aprotic solvents such as DMF and THF gave comparatively low selectivity and reactivity. With increasing the temperature from −40 °C to 80 °C in alcoholic solvent, the stereoselectivity increased to reach a maximum at 20–40 °C, then decreased. The effects of solvent and temperature on the stereoselectivity were discussed.
Facile Preparation of Optically Active Bicyclo[3.3.1]nonane-2,6-diol and 3,3,7,7-Tetramethylbicyclo[3.3.1]nonane-2,6-diol by Enzyme-Catalyzed Hydrolysis, and Enantiomer Recognition Behavior of Crown Ethers and Podands Having These Diols as a Chiral Subunit
Authors: Naemura Koichiro , Matsumura Takahisa , Komatsu Masanori , Hirose Yoshiki , Chikamatsu Hiroaki
Published: July 2006

Hydrolysis of 2,6-diacetoxybicyclo[3.3.1]nonane (5) using lipase from Candida cylindracea gave (+)-(1S,2R,5S,6R)-6-acetoxybicyclo[3.3.1]nonan-2-ol (4) with 81% e.e. and (−)-(1R,2S,5R,6S)-5 with 95% e.e., and pig liver esterase-catalyzed hydrolysis of 2,6-diacetoxy-3,3,7,7-tetramethylbicyclo[3.3.1]nonane (9) afforded (−)-(1S,2R,5S,6R)-3,3,7,7-tetramethylbicyclo[3.3.1]nonane-2,6-diol (7) with 96% e.e. and (+)-(1R,2S,5R,6S)-9 with 86% e.e. By lithium aluminum hydride reduction, (+)-4 and (−)-5 were converted to (+)-bicyclo[3.3.1]nonane-2,6-diol (3) and (−)-3 with high optical purity, respectively, and (+)-7 was obtained from (+)-9. Using these optically active diols 3 and 7 as a chiral subunit, optically active crown ethers and podands were prepared and their enantiomer recognition behavior was evaluated by the enantiomer differential transport of (±)-1,2-diphenylethylamine and methyl ester of (±)-phenylglycin hydrochloride through bulk liquid membrane.
Efficient Reduction of Triphenylmethanol to Triphenylmethane by 9,10-Dihydro-10-methylacridine in the Presence of Perchloric Acid
Authors: Ishikawa Masashi , Fukuzumi Shunichi , Goto Tatsushi , Tanaka Toshio
Published: July 2006

Reduction of triphenylmethanol (Ph3COH) to triphenylmethane by an NADH model compound, 9,10-dihydro-10-methylacridine (AcrH2), proceeds very efficiently in the presence of perchloric acid (HClO4) in acetonitrile at 298 K via hydride transfer from AcrH2 to triphenylmethyl cation (Ph3C+) which is formed by the dehydration of Ph3COH with HClO4. Mechanisms of hydride transfer reactions from NADH model compounds to Ph3C+ are also discussed.
Preparation of Optically Pure α-Alkyl β-Hydroxy Nitriles by the Bakers’ Yeast Reduction
Authors: Itoh Toshiyuki , Fukuda Tsuneyasu , Fujisawa Tamotsu
Published: July 2006

The bakers’ yeast reduction of 2-alkyl-3-oxobutyronitrile gave optically pure 2-alkyl-3-hydroxybutyronitriles. Especially 2-phenyl-3-oxobutyronitrile gave only syn diastereomer of 2-phenyl-3-hydroxybutyronitrile in high optical yield.
Photoelectrochemical Properties of Thin Films of Zinc Porphyrin Derivatives with Pyridyl Group
Authors: Takahashi Kohshin , Komura Teruhisa , Imanaga Hiroto
Published: July 2006

The cathodic photocurrents of the film electrodes of ZnPyP3P(3) and ZnPyP3P(4), (PyP3P(n), 5-(2-, 3-, and 4-pyridyl)-10,15,20-triphenylporphyrin, where (n) denotes the position of free bond of pyridyl group), were almost four times larger than that of ZnTPP (TPP, 5,10,15,20-tetraphenylporphyrin) in 0.01 mol dm−3 quinhydrone aqueous solution at pH 5. On the other hand, the very small anodic photocurrent was observed with the film electrodes of ZnTPyP(3) and ZnTPyP(4) (TPyP(n),5,10,15,20-tetra(2-, 3-, and 4-pyridyl)porphyrin). The photoelectrochemical properties of ZnPyP3P(2) and ZnTPyP(2) were distinct from those of other structural isomers, but approximately similar to those of ZnTPP. The conductivities of ZnPyP3P(n) films were about three oders of magnitude larger than those of ZnTPP and ZnTPyP(n) films. It was found from the absorption and resonance Raman spectra that the pyridyl group in porphyrin coordinated to zinc in another porphyrin in the solid films as well as in toluene and dichloromethane solutions. The molecular arrangement of zinc porphyrin in the solid film probably influenced the photoelectrochemical properties and the conductivity.
Analysis of Cyclic Voltammograms for Polypyrrole-as-Deposited Pt/poly[tris(4-vinyl-4′-methyl-2,2′-bipyridine)ruthenium(II) perchlorate] Electrodes
Authors: Murao Kenji , Tanaka Naoki , Suzuki Kazuhiro
Published: July 2006

Oxidation waves in cyclic voltammograms (CVs) observed during repeated potential cyclings of polypyrrole-as-deposited Pt/poly-1 electrodes (poly-1: poly[tris(4-vinyl-4′-methyl-2,2′-bipyridine)ruthenium(II) perchlorate]) in 0.1 M TBAP/acetonitrile, that lead to the bilayer (BL) electrochemistry, have been quantitatively analyzed. As the potential cycling is repeated, the CV change occurs, i.e., decrease of the peak current and positive shift of the peak potential. This is shown to be the result of logarithmic decrease in the complementary charge transfer coefficient β in the totally irreversible thin-layer (TITL) electrochemistry. kTL° (standard rate constant for polypyrrole oxidation) and CTL° (initial concentration of the reduced sites in polypyrrole) have been determined to be 5.50×10−9 cm mol−1 s−1 and 3.15×10−3 mol cm−3, respectively, by fitting CV data to the theory of the TITL model. The subsequent onset and growth of the CV waves in the higher potential region are explained as being due to progressive partitioning of polypyrrole sites from the TITL mode to the BL mode in which polypyrrole sites are oxidized. The partition coefficient θ, defined as the ratio of polypyrrole sites oxidized in the BL mode to all the polypyrrole sites, has been found to approximately depend on the logarithm of β. In the BL mode, a linear relationship is found between peak current and peak potential. Simulation of the CV waves has been performed based on the theoretical models of TITL and BL electrochemistry, and has revealed that a model assuming separation of polypyrrole sites into the TITL and BL modes prior to each cyclic sweep explains the occurrence of the significantly separated current peaks in both modes. These results are discussed in terms of Electrochemically driven Phase Separation (ECPS), in which the decrease in β is directly related to the separation of the mixed poly-1 and polypyrrole phase.
Methanol-Incorporated Photoaddition of N-Methyl-9,10-phenanthrenedicarboximide to Alkenes. Addition at Carbonyl and Phenanthrene-Ring Carbon Atoms
Authors: Kubo Yasuo , Nanba Mikako , Hayashi Etsuko , Araki Takeo
Published: July 2006

Irradiation of acetonitrile–methanol (2:1 v/v) solutions of N-methyl-9,10-phenanthrenedicarboximide (3) with alkenes 5a–g gave methanol-incorporated adducts (9c–f) at a carbonyl carbon atom in 3, those (10c,f) at a phenanthrene-ring carbon atom, and a methanol-adduct 11g to alkene 5g, together with products 4, 6b,e–g, 7b,e–g, and 8e,f obtained by the photoreactions in benzene. The concentration effect of alkenes 5e,f on yields of products 6e,f, 7e,f, 8e,f, 9e,f, and 10f showed that both 9e,f and 10f arose from a relatively short-lived singlet excited state of 3. The values of the free-energy change associated with an electron transfer (ΔGet) from alkenes 5a–d,g to the singlet excited state of 3 and fluorescence quenching rate constants support a photochemical electron transfer mechanism for the methanol-incorporated addition. Both LiClO4 and BU4NClO4 caused only slight decreases in the relative ratios 10c/9c indicating that both the methanol-incorporated addition at the phenanthrene-ring carbon atom and that at the carbonyl carbon atom might arise from a contact ion pair state. The fact that the methanol-incorporated addition at the arene-ring carbon atom was observed only in the reaction of 3 in a series of N-methylarenedicarboximides, possessing a five-membered imide ring, is interpreted on the basis of the spin density of the radical anions of the imides derived from the photochemical electron transfer.
Homologation of the Side Chain of 2-Nitrotoluene. Synthesis of a Tryptophan Precursor
Authors: Tanaka Hideo , Murakami Yasuo , Torii Sigeru
Published: July 2006

2-(2-Nitrophenyl)-1,3-propanediol (2) was selectively converted to 2-(2-nitrophenyl)propenal (3) by the use of a mixture of dicyclohexylcarbodiimide (DCC) and dimethyl sulfoxide in benzene, while 2-nitrobenzoic acid was obtained by the oxidation of the diol 2 with sodium periodate in the presence of a catalytic amount of ruthenium dioxide or with chromic acid. The enal 3 was subjected to further transformation to afford a potent tryptophan precursor and some useful indole derivatives.
Synthetic Photochemistry. XLVI. Cycloaddition of exo, endo-2,7-Bis(methoxycarbonyl)-11,12-dioxatetracyclo[6.2.1.13,6.02,7]dodeca-4,9-diene and Conjugated Enones and p-Quinones
Authors: Tian Guan Rong , Mori Akira , Kato Nobuo , Takeshita Hitoshi
Published: July 2006

Photocycloaddition of exo,endo-2,7-bis(methoxycarbonyl)-11,12-dioxatetracyclo[6.2.1.13,6.02,7]dodeca-4,9-diene with conjugated enones and p-quinones occurred exclusively at the exo-addition moiety to give [2+2]cycloadducts. From cyclohexenone, all four possible photoadducts were obtained. A single photoadduct from cyclopentenone was a cis-transoid-cis isomer. Upon thermolysis, cyclobutene derivatives were formed from these photoadducts. An acid treatment of oxetane derivatives derived from photoadducts of p-quinones afforded Michael adducts instead of dienone–phenol rearrangement products.
Crystal Structure of an 8,5′-Iminocarbonyloxy-Bridged Guanine Nucleoside Methanol Solvate
Authors: Minamoto Katsumaro , Shiomi Niro , Kondo Kazumoto , Eguchi Shoji , Honda Masako , Katayama Chuji , Katayama Atsushi , Tanaka Jiro
Published: July 2006

The crystal structure of 8,5′-[(allylimino)carbonyloxy]-2-N-dimethylaminomethylene-9-(2′,3′-O-isopropylidene-β-d-ribofuranosyl)guanine (2a) methanol solvate was determined by X-ray analysis. Its base-sugar torsion angle conforms to the CD spectral behavior of the partially deprotected compound 2b in the sense of anti-conformation.
Regioselective Reaction of Oxiranes with S-Phenyl Thioesters Catalyzed by Quaternary Onium Salts or Crown Ether–Metal Salt Complexes
Authors: Iizawa Takashi , Goto Akira , Nishikubo Tadatomi
Published: July 2006

Regioselective addition reactions of 2-substituted oxiranes with S-phenyl thioesters gave 2-aceyloxy-1-phenylthio derivatives in high yield using some 18-crown-6–metal complexes as well as tetrabutylammonium salts as a catalyst under relatively mild conditions.
Methylviologen-Accelerated Photoreduction of Tris(acetylacetonato)cobalt(III) with 1-Benzyl-1,4-dihydronicotinamide
Authors: Yamashita Kohichi , Kajiwara Shûta , Ohkubo Katsutoshi
Published: July 2006

The photoreduction of tris(acetylacetonato)cobalt(III) (Co(acac)3) by 1-benzyl-1,4-dihydronicotinamide (BNAH) was examined with or without methylviologen in the wavelength range of 340–410 nm. The reaction rate of electron transfer from BNAH to Co(acac)3 was considerably enhanced by methylviologen, especially, in lower polar environments; The weaker the hydrophobic interaction between BNAH and the substrate become, the more effectively methylviologen acts as an electron mediator for the above photoreaction. The reaction mechanism is also discussed with particular reference to the participation of the electron mediator in the elementary steps of the present photoinduced reaction.
Prediction of Soil Sorption Coefficients of Hydrophobic Organic Pollutants by Adsorbability Index
Authors: Okouchi Shoichi , Saegusa Hisayoshi
Published: July 2006

The adsorbability index proposed by Abe et al. to predict the activated carbon adsorption of organic compounds from aqueous solution was well correlated with the soil sorption coefficients of polycyclic aromatic hydrocarbons (PAHs), alkylbenzenes, chlorobenzenes, chlorinated alkanes and alkenes, heterocyclic and substituted PAHs, and halogenated phenols. The adsorbability index was also found to be well correlated with the first-order molecular connectivity index and the total molecular surface areas of these compounds.
XPS Study of Binuclear Mo(V) Complexes with Di-μ-oxo, μ-Oxo-μ-sulfido, and Di-μ-sulfido Bridges
Authors: Takahashi Hideaki , Shibahara Takashi , Yamamoto Yoshihisa
Published: July 2006

X-Ray photoelectron spectroscopy (XPS) was applied to three binuclear molybdenum(V) complexes of di-μ-oxo-, μ-oxo-μ-sulfido-, and di-μ-sulfido-bis[(cysteinato)oxomolybdate(V)]2−, [Mo2(μ-O)x(μ-S)yO2(cys)2]2− (x=2, y=0; x=y=1; and x=0, y=2), and the electronic state for Mo atom of the (μ-O)2 bridge, (μ-O, μ-S) bridge and (μ-S)2 bridge complexes was studied. It has been found that the binding energy of the Mo 3d5⁄2,3⁄2 peaks shifts to a lower value by at most 0.5 eV with increasing the number of μ-S bridges from 0 to 2. On the other hand, those of O 1s, C 1s, N 1s, and S 2s peaks are not significantly affected by bridge substitution. The change in the electronic state of Mo atoms is discussed in terms of the low electronegativity of the S atom.
Solubilities and Dissolution States of a Series of Symmetrical Tetraalkylammonium Salts in Water
Authors: Nakayama Haruo , Kuwata Hiromi , Yamamoto Norikazu , Akagi Yutaka , Matsui Hiroshi
Published: July 2006

The solubilities of a series of symmetrical tetraalkylammonium salts, R4NX (R=CH3–n-C8H17, including i-C4H9 and i-C5H11; X=Cl, Br, I, NO3, and ClO4), in water have been determined over the temperature range between 5 and 45 °C. The solubilities of these salts were found to be strongly dependent upon both the chain length of R of the R4N+ cation and upon the partial molar volume of the X− anion. It has been concluded that these solubilities are closely related with the stability of a “cage-like” water structure, which is presumably formed around the R4N+ cation in the solution. A thermodynamic interpretation of the solubility of the R4NX salts was made by using some thermodynamic properties obtained by a differential scanning calorimetry, together with the enthalpy of the solution calculated from the temperature dependence of the solubility.
THE CRYSTAL AND MOLECULAR STRUCTURE OF CHLOROGLYCYL GLYCINATOCOPPER(II) MONOHYDRATE
Authors: Shiro Motoo , Nakao Yasuo , Yamauchi Osamu , Nakahara Akitsugu
Published: July 2006

Crystals of chloroglycylglycinatocopper(II) monohydrate crystallized from acid solution are monoclinic, space group P21/c, with 8 formula units in a cell. The copper(II)-glycylglycine chelate has a dimeric structure, in which the peptide is bonded to two copper atoms - to one through the terminal nitrogen and the peptide oxygen and to the other through the terminal oxygen. The copper atom is five-coordinated and has a distorted square pyramidal coordination polyhedron.
BIOSYNTHESIS OF TRITERPENOIDS. THE STEREOCHEMISTRY OF THE SQUALENE FORMATION AND ITS CYCLIZATION TO β-AMYRIN
Authors: Suga Takayuki , Shishibori Tsuyoshi , Kimoto Sanae
Published: July 2006

The distribution of deuterium in squalene and β-amyrin biosynthesized from [6-D3]-mevalonic acid in Pisum sativum has been analyzed by NMR spectroscopy. It was thus proved that the cis-terminal methyls of squalene and the 4β-methyl group of β-amyrin are stereospecifically derived from the 3-methyl group of mevalonic acid.
STRUCTURE OF PHOTO-ADDUCT BETWEEN 1,2-NAPHTHOQUINONE AND XANTHENE
Authors: Maruyama Kazuhiro , Takuwa Akio
Published: July 2006

Photochemical reaction between 1,2-naphthoquinone and xanthene was studied. By a smooth reaction photo-adduct is produced as white needles after irradiation for several hours. Structure of the photo-adduct was determined as (7) through the investigation by PMR, IR, Mass, and elemental analysis. The photo-adduct between the o-quinone and the hydrogen donor having such a type of structure have never been reported so far. This reaction was examined from the dynamical point of view using CIDNP technique and the results substantiated further the structure (7).
INSERTION OF ETHOXYCARBONYLNITRENE TOWARD AXIAL AND EQUATORIAL C–H BONDS
Authors: Shingaki Tadao , Inagaki Masao , Torimoto Noboru , Takebayashi Matsuji
Published: July 2006

Ethyl azidoformate was decomposed on heating or by irradiation with UV in trans- and cis-1,4-dimethylcyclohexanes. Relative reactivities of the nitrene insertion toward axial and equatorial C–H bonds were calculated from the results. It was found that the reactivities toward axial C–H bonds were less than those of equatorial C–H bonds.
OXIDATION OF HEXAHYDROPYRIMIDINES INTO 3,4,5,6-TETRAHYDROPYRIMIDINIUM SALTS IN THE PRESENCE OF PALLADIUM CATALYST
Authors: Tsuji Tadakazu , Muraoka Masako
Published: July 2006

Treatment of 5-amino- and 5-nitro-5-methyl-1,3-disubstituted hexahydropyrimidines with palladium chloride gave the corresponding 3,4,5,6-tetrahydropyrimidinium chlorides, which were also obtained from the air oxidation of hexahydropyrimidine hydrochlorides in the presence of palladium black.
THE CYCLIZATION REACTION OF 5-BROMO-o-CRESOTIC ACID WITH PARAFORMALDEHYDE
Authors: Asaoka Tadatomo , Shinoda Misao , Shimasaki Choichiro
Published: July 2006

The reaction of 5-bromo-o-cresotic acid (I) with paraformaldehyde using cone sulfuric acid as a catalyst at 0–5°C for 3–4 hr yielded a new cyclic compound 6-bromo-8-methyl-4-oxobenzo[d]-1,3-dioxane (II). Similar results were obtained in the cases of 5-chloro-o-cresotic acid and 5,5-methylene-di-o-cresotic acid.
CONFIGURATIONAL ASSIGNMENT OF α-PHENYL-α,N-DIMETHYLNITRONES BY A LANTHANIDE SHIFT REAGENT IN PROTON MAGNETIC RESONANCE SPECTROSCOPY
Authors: Yoshimura Yohko , Mori Yutaka , Tori Kazuo
Published: July 2006

The ketonitrones, α-phenyl- and α-p-tolyl-α,N-dimethylnitrones (IIa and IIb, respectively), have been determined to be E isomers by application of a paramagnetic lanthanide shift reagent and benzene-induced solvent shifts in PMR spectroscopy.
FORMATION OP TITANIC OXIDES OF ANATASE, BROOKETE AND RUTILE TYPES BY AERIAL OXIDATION OF TITANOUS SOLUTIONS
Authors: Kiyama Masao , Akita Toshikazu , Tsutsumi Yuji , Takada Toshio
Published: July 2006

Aerial oxidation of titanous solutions has been carried out at temperatures between 60° and 95°C. A desired one of titanic oxides of anatase, brookite and rutile types, can be obtained from strongly acidic solutions by selection of the kind and concentration of anions present and temperature.
A NEW ACID CATALYZED OXIDATION OF SOME ACETYLENIC COMPOUNDS WITH SELENIUM DIOXIDE
Authors: Sonoda Noboru , Yamamoto Yuji , Murai Shinji , Tsutsumi Shigeru
Published: July 2006

It was found that oxidation of some acetylenic compounds with selenium dioxide was easily proceeded in the presence of catalytic amount of sulfuric acid. The oxidation took place mainly at the triple bond, and α-keto acid or α-diketone was isolated as a main product.
EMISSION SPECTRA OF TOLUENE AND ANISOLE BY CONTROLLED ELECTRON IMPACT
Authors: Ogawa Teiichiro , Tsuji Masaharu , Toyoda Minoru , Ishibashi Nobuhiko
Published: July 2006

The emission spectra of toluene and of anisole were observed by exciting them by controlled electron impact up to 300 V. A characteristic band of the aromatic hydrocarbon was observed in both cases.
X-RAY PHOTOELECTRON SPECTRA OF EVAPORATED NICKEL EXPOSED TO O2 AND H2O
Authors: Kishi Kosaku , Ikeda Shigero
Published: July 2006

Binding energies of Ni2p3⁄2, and Ols electrons were measured by X-ray photoelectron spectrometer during the interaction of evaporated nickel with O2 and H2O. Two kinds of peaks were obtained for both oxygen and nickel of the surface species formed. On the reaction of the surface species with H2O, electron transfer was observed.
THE OPTICAL RESOLUTION OF Dl-AMINO ACID MENTHYL ESTER DERIVATIVES BY PAPER CHROMATOGRAPHY
Authors: Akiyama Isamu , Onaya Masaji , Hayakawa Akira , Tsuzuki Yojiro
Published: July 2006

Several Dl-amino acid menthyl ester hydrochlorides were synthesized and attempted to resolve by means of paper chromatography with various buffer solutions. It was found that the three amino acid (Phe, Trp, and Tyr) derivatives were completely resolved with “CM-Cellulose” paper.
PSEUDOCONTACT SHIFT IN Eu(III) COMPLEXES, II. A SIMPLE THEORY FOR COMPLEXES OF C3h, D3h OR C3v POINT SYMMETRY
Authors: Sakaguchi Ushio , Yamasaki Akira , Fujiwara Shizuo
Published: July 2006

An approximate equation has been obtained for the pseudocontact shift in tris-chelated europium(III) complexes with C3h, D3h, or C3v symmetry. The crystal field energies have been calculated as a first-order perturbation on the spin-orbit levels.
SENECIO ALKAILOIDS. THE SYNTHESIS AND CONFIGURATION OF (±)-LATIFOLIC ACID
Authors: Matsumoto Takashi , Okabe Tetsuaki , Fukui Kenji
Published: July 2006

(±)-Latifolic acid and its three (±)-stereoisomers have been synthesized from dimethyl 1-acetyl-2-methylsuccinate. The synthetic (±)-2,cis-dimethyl-trans-3-hydroxy-cis-3-carboxybutyrolactone was shown to be identical with natural latifolic acid.
SYNTHESIS OF STANNOUS CHELATE COMPOUNDS
Authors: Wakeshima Ikuko , Kijima Ichiro
Published: July 2006

The synthesis of a novel type of stannous compounds was studied. The products are distillable and have high solubilities in organic solvents. The structures of the product were examined by tin analysis, molecular-weight determination, and studies of the IR and NMR spectra.
ZIEGLER-NATTA PROPYLENE POLYMERIZATION IN GAS PHASE: PRODUCTION OF HIGHLY ISOTACTIC POLYMERS
Authors: Doi Yoshiharu , Okura Ichiro , Keii Tominaga
Published: July 2006

The isotacticities of the polypropylenes produced with TiCl3–AlEt3 catalyst without solvent were 6∼7% higher than those obtained in the case with n-heptane solvent. In the case of TiCl3–AlEt2Cl catalyst there was no such a difference due to the presence of the solvent.
SOLID PHASE PEPTIDE SYNTHESIS BY OXIDATION-REDUCTION CONDENSATION. ATTACHMENT OF VARIOUS AMINO ACIDS AND PEPTIDE FRAGMENTS TO THE HYDROXYMETHYL RESIN
Authors: Matsueda Rei , Kitazawa Eiichi , Maruyama Hiroshi , Takahagi Hidekuni , Mukaiyama Teruaki
Published: July 2006

An attachment of the first amino acid to the resin in solid phase method by oxidation-reduction condensation was investigated. Various amino acids and peptide fragments were attached to the hydroxymethyl resin and chain-lengthening of these aminoacyl resins with amino acids or peptide fragments was successfully achieved by the same procedure.
VINYL POLYMERIZATION. 292. A MACROMOLECULAR EFFECT OBSERVED BY THE POLYMERIZATION OF METHYL METHACRYLATE INITIATED WITH THE SYSTEM OF CELLULOSE, Cu(II)-ION AND WATER
Authors: Imoto Minoru , Otsuka Saburo , Ouchi Tatsuro
Published: July 2006

The system of cellulose, water and Cu(II)-ion can polymerize MMA through a radical mechanism. The rate of polymerization, Rp, is expressed by the equation,

Rp = k [Cellulose]n[MMA]1→0

The value of n decreases from 1.0 to 0.5 with the decrease of the degree of polymerization of the cellulose.
NEGATIVE PHOTOCONDUCTION IN SOLUTION DUE TO PHOTOEJECTION OF ELECTRON FROM p-BENZOQUINONE ANION TO TETRAMETHYL-p-PHENYLENEDIAMINE CATION
Authors: Imura Takeshi , Nakata Jun-ichi , Kawabe Kazuo
Published: July 2006

Photolysis of a solution of a strong electron donor and acceptor in tetrahydrofuran caused decrease of the electric conductivity of the solution. The negative photoconduction was presumably due to photoionization of the anion which exists slightly on dissociation equilibrium, and to subsequent trapping of the solvated electron by the cation of the donor.
SYNTHESIS OF THIOCYANATES BY OXYTHALLATION OF OLEFINS
Authors: Mitani Hiroshi , Ando Takashi , Yukawa Yasuhide
Published: July 2006

A convenient method to introduce a thiocyano group into an olefin with thallium triacetate is described. The reaction proceeds via oxythallation, replacement of an acetate ion with a thiocyanate ion, and dethallation, successively.
MOLECULAR-SIEVE TYPE SORPTION ON ALKALI GRAPHITES
Authors: Watanabe Kazuo , Kondow Tamotsu , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The general tendency of the sorption exhibited by 2nd-stage alkali graphites, C24K, C24Rb and C24Cs may be most conveniently interpreted by a molecular-sieving effect, since the sorption characteristics are dependent on the size of the gaseous molecules and of the intercalated alkali atoms.
THE PHOTOCYCLOADDITION OF ACENAPHTHYLENE WITH TETRACYANOETHYLENE
Authors: Shirota Yasuhiko , Nagata Jun-ichiro , Mikawa Hiroshi
Published: July 2006

Irradiation of a solution of acenaphthylene and tetracyanoethylene yielded the cycloadduct. The excited singlet acenaphthylene is suggested to be the reactive species.
EXCIMER EMISSIONS OF SOME AROMATIC VINYLPOLYMERS
Authors: Yokoyama Masaaki , Tamamura Toshiaki , Nakano Takeshi , Mikawa Hiroshi
Published: July 2006

The emission spectra of poly-3-vinylpyrene (PVPy), poly-3-pyrenylmethylvinylether (PPMVE), and poly-9-vinylacridine (PVAc) in solution were measured at room, dry-ice, and liq. N2 temperatures. New observations of excimer fluorescences of these polymers could be obtained. Lifetimes of excimer fluorescences were measured in pulse method with excitation of N2 gas laser; 160, 66, and 31 nsec for PVPy, PPMVE, and PVAc, respectively. Emission spectra of PVPy and PVAc almost exclusively consist of excimer fluorescences even at dry-ice temperature on the contrary to PPMVE.
STUDY OF RANEY NICKEL CATALYSTS BY ELECTRON MICROPROBE X-RAY ANALYZER
Authors: Yasumura Jiro , Nakabayashi Ichiro
Published: July 2006

On the basis of several observations of laminated Raney nickel catalysts with an electron microprobe X-ray analyzer, it is concluded that the activity of the catalysts is seemingly correlated to the composition of Raney nickel alloys, and that the active centers are distributed probably at random on the surface of the catalysts.
A NOVEL TRANSANNULAR REACTION OF 2,4,6-CYCLOOCTATRIEN-1-ONE
Authors: Ogawa Masashi , Takagi Makoto , Matsuda Tsutomu
Published: July 2006

Esters of 2,5-cyclohexadienylacetic acid were formed in the reaction of 2,4,6-cyclooctatrien-1-one with alkoxides in alcohols. A ring contraction concerted with a transannular hydrogen transfer to C(4) position from an intermediate hemiacetal was proposed as a plausible pathway on the basis of deuterium distribution in the product.
ACETOPHENONE IN THE GAS PHASE OXIDATION OF ETHYLBENZENE WITH PALLADIUM CATALYST
Authors: Nakamura Seishiro , Tamura Masuhiko , Yasui Teruo
Published: July 2006

Acetophenone was obtained selectively accompanied by small amounts of styrene and carbon dioxide in the gas phase oxidation of ethylbenzene with palladium catalyst below 140°C. Acetophenone was postulated to form from the direct oxidation of ethylbenzene since styrene was not oxidized under similar conditions even at higher temperature.
THE ALKYLATION OF 1,3,5-TRITHIANES
Authors: Fukunaga Michio , Sugawara Tadashi , Oki Michinori
Published: July 2006

A method of synthesis of 1,3,5-trithiane derivatives which carry the desired number of methyl groups is described. Anions derived from 1,3,5-trithianes are found to undergo fast proton exchange with 1,3,5-trithianes if the latters carry a methylene group placed between two sulfur atoms.
MAGNETIC PROPERTIES OF ORGANIC STABLE RADICALS. IV. DPPH AND ITS SOLVENT COMPLEXES
Authors: Fujito Teruaki , Enoki Toshiaki , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo
Published: July 2006

Magnetic susceptibility of organic stable radicals, DPPH and its solvent complexes has been measured. Susceptibility of solvent free DPPH shows a maximum at 11°K and is well fitted to the pair model (δ⁄k=17.64°K). DPPH·BZ has a χmax at 0.65°K but remains constant down to 0.1°K. DPPH·1/4CCl4 has two Weiss-constants: θHigh=−26.0°K and θLow=−0.3°K. Spin concentration of the last complex in low temperature range (below 4.2°K) is a half of that of high temperature range (above 30°K).
REACTION OF PERFLUORO-4-METHYLPENTENE-2 WITH SECONDARY AMINES
Authors: Tsukamoto Goro , Ishikawa Nobuo
Published: July 2006

Perfluoro-4-methylpentene-2 [1] , an asymmetrical internal perfluoroolefin, reacted with secondary amines such as diethylamine or piperidine to give a terminal enamine [2], which was easily hydrolyzed to the corresponding amide [3]. The reaction mechanism was discussed.
DYNAMIC STEREOCHEMISTRY OF π-ALLYLIC Pd(II) α-AMIROACETATE COMPLEXES
Authors: Nakagawara Yoshihiro , Kikukawa Kiyoshi , Takagi Makoto , Matsuda Tsutomu
Published: July 2006

A variety of π-allylic Pd(II) aminoacetate complexes were synthesized, and their temperature dependent NMR study revealed the presence of diastereoisomers which are in dynamic equilibrium by π-allyl rotation mechanism.
4-DIPHENYLMETHYLENE-1,2-DIPHMYLBUTATRIAFULVALENE-3,5-DIONE
Authors: Toda Fumio
Published: July 2006

The title butatriafulvalenedione (V) was prepared by the condensation of diphenylmethylenecyclobutane-1,3-dione (IV) with diphenylcyclopropenone. The spectral data of V were discussed. V was dissolved in methanolic potassium hydroxide in the form of the enolate anion (VI), and the acidification of the solution recovered V.
A NOVEL SYNTHESIS OF 5-OXO- AND 7-OXO-PYRIDO[2,3-d]PYRIMIDINES
Authors: Ogura Haruo , Sakaguchi Masakazu
Published: July 2006

5-Oxo- (VI) and 7-oxo-pyrido[2,3-d]pyrimidines (IV) were synthesized from 6-amino-1,3-dimethyluracil derivatives (I) with dimethyl acetylenedicarboxylate or diketene. Analogously, 5-oxothiopyrano[2,3-d]pyrimidine (VIII) was obtained from VII and diketene.
THE CHEMISTRY OF PHENALENIUM SYSTEM IX. REACTION OF LITHIUM PHENALENIDE WITH 1,2-DISUBSTITUTED 3,3-DICHLOROCYCLOPROPENES
Authors: Murata Ichiro , Nakazawa Tomoo , Shima Keiko
Published: July 2006

Reaction of lithium phenalenide (2) with 1,2-di-n-propyl-3,3-dichlorocyclopropene (3: R=n-C3H7), and with l,2-diphenyl-3,3-dichloro-cyclopropene (3: R=C6H5.) in ether under nitrogen gives rearranged products, 1,3-di-n-propylpyrene (4) and 10-phenyl-10-phenylethynylphenafulvene (5), respectively.
POLYMERIZATION OF CYOLOPENTADIENE WITH PERCHLORIC ACID
Authors: Kohjiya Shinzo , Terada Akira , Yamashita Shinzo
Published: July 2006

Cyclopentadiene was polymerized in toluene or in methylene chloride with perchloric acid. Kinetic features seemed to be very simple and propagation rate constants were estimated according to the kinetics of Pepper et al. The values of kP were 6.7 l/mol sec. in methylene chloride and 0.83 l/mol sec. in toluene.
[6]METACYCLOPHANE AND RELATED COMPOUNDS
Authors: Hirano Shigeo , Hiyama Tamejiro , Fujita Shinsaku , Nozaki Hitosi
Published: July 2006

The title phane (IV) with the shortest aliphatic bridge among [n]metacyclophanes has been obtained from the enone I. The PMR spectra indicate the pseudorotation of the hexamethylene chain occurring with abnormally high energy barrier of 11.1 kcal/mol at −31.5°C for IV and 12.4 kcal/mol at −4.5°C for its 12-bromo derivative (III).
DIFFERENCE BETWEEN VOLTAGE AND CURRENT FOLLOWER MODES AS CURRENT MEASURING DEVICE IN ELECTROCHEMICAL OSCILLATORY SYSTEM
Authors: Saito Atsuyoshi
Published: July 2006

It was found that polarograms of the electrochemical oscillatory systems showed anomalous current increase and oscillation in a narrow region of potentials in the descending branch of the current-voltage curves when the voltage-follower mode was used as a current measuring device, while the usual polarograms were observed by the current-follower mode.
SYNTHESIS OF ANOMERIC METHYL 6-O-(l-MYCAROSYL)-β-d-GLUCOSAMINIDES
Authors: Koto Shinkiti , Yago Kazuo , Zen Shonosuke , OMura Satoshi , Hata Toju
Published: July 2006

Anomeric isomers of methyl 2-amino-2-deoxy-6-O-(2,6-dideoxy-3-C-methyl-l-ribo-hexopyranosyl)-β-d-glucopyranoside (VI) were synthesized by the condensation of methyl 2-deoxy-2-(2,4-dinitroanilino)-β-d-glucopyranoside with 3,4-O-carbonyl-2,6-dideoxy-l-ribo-hexopyranosyl chloride (III), and subsequent removal of blocking groups.
HEAT CAPACITY ANOMALY IN THE CRYSTALLINE ORGANIC FREE RADICAL, p-Cl-BDPA
Authors: Yamauchi Jun , Adachi Kimio , Deguchi Yasuo
Published: July 2006

The heat capacity has been measured on polycrystalline sample of 1,3-bisdiphenylene-2-p-chlorophenyl-allyl (abbreviated as p-Cl-BDPA). The sharp heat capacity anomaly was observed at 3.25 K, which may imply a paramagnetic-antiferromagnetic phase transition. This phenomenon accords well with the other results obtained from the susceptibility, ESR, and NMR measurements.
RESONANCE RAMAN SPECTRUM OF THE STARCH–IODINE COMPLEX
Authors: Tasumi Mitsuo
Published: July 2006

Resonance Raman spectrum of the starch–iodine complex was observed in dilute aqueous solution. Three Raman bands observed at 163, 115, and 56 cm−1 are assigned, respectively, to the antisymmetric stretching, symmetric stretching, and bending vibrations of the I3− ion aligned linearly in the helical starch molecule.
STUDIES OF PHOTOSENSITIVE RESINS V. THE PHOTO-DECOMPOSITION MECHANISM OF O-NAPHTHOQUINONE DIAZIDES
Authors: Nakamura Kenichiro , Udagawa Sakae , Honda Kenichi
Published: July 2006

Photochemical decomposition of the naphthoquinone-diazide resists has been investigated from the behaviors of their excited states and from the resulting intermediates. The exposure of naphthoquinone diazide sulfonic acid solution to the flash irradiation gives rise to a new strong absorption in a region near 350 nm, which is identified as the ketene intermediates formed during the photo-decomposition process.
LEUCOTHOL A, AN ANTHRADITERPENOID FROM LEUCOTHOE GRAYANA MAX.
Authors: Furusaki Akio , Hamanaka Nobuyuki , Miyakoshi Hidehiro , Okuno Toshikatsu , Matsumoto Takeshi
Published: July 2006

The structure of leucothol A, C20H30O3, a minor constituent of Leucothoe grayana Max., has been determined as 2 by means of X-ray crystallographic analysis. Leucothol A is the first example of anthraditerpenoid.
THE USE OF 8-ACYLOXYQUINOLINE METAL COMPLEX IN THE ACYLATION REACTION AND THE KETONE SYNTHESIS. THE METAL ION PROMOTED REACTIONS OF 8-ACYLOXYQUINOLINE I.
Authors: Sakan Takeo , Mori Yutaka
Published: July 2006

8-Acyloxyquinoline metal complexes were discussed of their possible use as an active acylating agent. In this connection, the reaction of 8-acyloxyquinolines with the Grignard reagent was found to be useful as a novel synthetic method for ketones.
PREPARATION OF CRYSTALLINE SALTS OF METHYLPHENAZINIUM RADICAL CATION
Authors: Takagi Yutaka , Akasaka Kazuyuki , Imoto Toshiaki , Kawai Hitomi , Ishizu Kazuhiko
Published: July 2006

A stable crystalline salt (e.g. perchlorate) of the methylphenazinium radical cation was prepared. The method is based on the photoreduction of phenazine methosulfate in acid solution containing oxalate or tartrate.
ENANTIOMERIC SHIFT DIFFERENCE INDUCED BY THE LANTHANIDE SHIFT REAGENT: ITS CORRELATION WITH ABSOLUTE CONFIGURATION OF α-AMINO ACIDS
Authors: Ajisaka Katsumi , Kamisaku Masako , Kainosho Masatsune
Published: July 2006

Chiral lanthanide shift reagents have been found to be applicable to the absolute configurational problem as well as to the direct determination of optical purities of α-amino acids.
ION-MOLECULE REACTIONS OF SULFUR IONS (4S0 AND 2D0 STATES) AND CARBONYL SULFIDE IONS IN CARBONYL SULFIDE SYSTEM
Authors: Matsumoto Akira , Misaki Toshiyuki , Okada Satoshi , Taniguchi Setsuo , Hayakawa Teruo
Published: July 2006

Ion-molecule reactions in pure COS have been studied using a pulsing method. The reactions including the excited S+ for S+2 formation have been identified and the rate constants measured. The fraction of the excited state present in the S+ ions formed at electron energy 18.3 eV was estimated to be 0.36.
HIGH SENSITIVITY DOSIMETRY BY 14CO2
Authors: Sato Shoichi , Kamegashira Naoki , Tanabe Hiromi , Sasuga Norihiko , Danno Akibumi , Shinagawa Mutsuaki , Tamura Takaaki , Naito Keiji
Published: July 2006

The gamma dose rate in a nuclear reactor has been measured by using 14CO2 as the gaseous chemical dosimeter. High sensitivity of the dosimetry was attained by measurements of the specific radioactivity of the radiolyzed product, 14CO relative to that of 14CO2.
HIGH SELECTIVITIES OF ZIRCONIUM OXIDE CATALYST FOR ISOMERIZATION OF 1-BUTENE AND DEHYDRATION OF sec-BUTANOL
Authors: Yamaguchi Tsutomu , Sasaki Hiroshi , Tanabe Kozo
Published: July 2006

Zirconium oxide catalyst gave a high product ratio, 7.3, of cis-2-butene/trans-2-butene from 1-butene and 90.2% of 1-butene in butenes formed from sec-butanol. Poisoning effect of n-butylaraine or carbon dioxide on the reactions suggested that the catalyst has both acidic and basic character.
REACTION OF o-BENZOQUINONE DI-IMINE WITH o-PHENYLENEDIAMINE
Authors: Nogami Takashi , Hishida Tadanori , Shirota Yasuhiko , Mikawa Hiroshi
Published: July 2006

o-Benzoquinone di-imine was obtained fairly stably in ether solution by oxidizing o-phenylenediamine with lead dioxide. The reaction of o-benzoquinone di-imine with o-phenylenediamine was studied spectrophotometrically, and o,o′-diaminoazobenzene and 1,4-dicyanobutadiene were found to be formed as the reaction products. The reaction scheme was discussed.
CYCLIZATION REACTION OF N-(HALOACYL)- OR N-(PHTHALOYLGLYCYL)HYDROXYAMINO ACID ESTERS WITH AMMONIA
Authors: Shin Chung-gi , Nanjo Katsumi , Yoshimura Juji
Published: July 2006

A new type of cyclization of β-methoxy derivatives of N-haloacyl-or N-phthaloylglycyl-α-hydroxyamino acid esters with ammonia to 2-carbamoyl-4-imidazolidone is described.
MAGNETIC SUSCEPTIBILITY OF LITHIUM 2,2′-DIPYRIDYLIDE IN ITS DIETHYL ETHER ADDUCT
Authors: Inoue Motomichi , Hara Ken-ichi , Horiba Tatsuo , Kubo Masaji
Published: July 2006

The magnetic susceptibility of the diethyl ether adduct of lithium 2,2′-dipyridylide was determined at temperatures between 4.2 and 300 K. The magnetic susceptibility conforms to the alternating linear Heisenberg model (alternation parameter, a = 0.8) and indicates that strong antiferro magnetic interaction (J⁄k=−80 K) operates between anion radicals.
RAMAN SCATTERING STUDY OF THE PHASE TRANSITION IN TIN(II) CHLORIDE DIHYDRATE
Authors: Morisaki Hiroshi , Kiriyama Hideko , Kiriyama Ryôiti
Published: July 2006

The Raman spectra of SnCl2·2H2O and its deuterated analogue were measured between 110 and 300 K. Of eight peaks observed, the band at 253 cm−1 showed a drastic change in its location below Ttr, indicating the presence of a lattice mode coupled with the hydrogen ordering in the O–H··O hydrogen bonded network.
TOTAL SYNTHESIS OF A 9-DESOXY-PROSTAGLAND IN
Authors: Guzmán Angel , Crabbe Pierre
Published: July 2006

The unsaturated ketone (1) is reduced catalytically into the saturated keto-derivative (2) . Further transformations allow to open the bicyclic intermediate (2) into the tri-substituted cyclopentane derivative (4). This is then converted by classical methods into the 9-desoxy-prostaglandin (8).
PHOTOSENSITIZED ISOMERIZATION OF THE STILBENES WITH THE URANYL ION
Authors: Matsushima Ryoka , Sakuraba Shukichi
Published: July 2006

Sensitized cis→ trans and trans→cis isomerization of the stilbenes with the uranyl ion occured efficiently without reduction of the uranyl ion in deoxygenated acetone with the irradiation of λ≥365 nm, while no direct isomerization (in the absence of the uranyl ion) took place under the similar conditions. Upon a long period irradiation both the sensitized cis→trans and trans→cis isomerization gave the same isomer ratio, trans/cis = 3, which is abnormally high compared to those reported for organic triplet-sensitized isomerization. Significant oxygen-quenching was found for the sensitized isomerization, while no significant oxygen effect was observed for the quenching of the uranyl emission by the stilbenes.
THE CRYSTAL STRUCTURE OF PICOLINIC ACID
Authors: Takusagawa Fusao , Shimada Akira
Published: July 2006

The crystal structure of picolinic acid was determined by a three-dimensional X-ray analysis. The molecules are linked by two symmetric double minimum hydrogen bonds with a small potential barrier, N–H–N and O–H–O,and form a zig-zag chain.
SECONDARY BATTERY USING THE ION-EXCHANGE CARBON FIBER AND AN AQUEOUS SOLUTION OF NaCl
Authors: Otani Sugio
Published: July 2006

New secondary battery having about 2V of the electromotive force was made by placing the ion-exchange carbon cloths as a positive and a negative electrodes in an aqueous solution of NaCl. The capacity of the battery using each l6g of electrodes was 0.46 A-hr in the case of continuous discharge of 0.02 A/dm2.
SYNTHESIS OF (±) -14-HYDROXY-12-ISOPROPYL-3-OXOPODOCARPA-1,8,11,13- AND (±)-14-HYDROXY-12-ISOPROPYL-1-OXOPODOCARPA-2,8,11,13–TETRAENES, AND (±)-12-HYDROXY-1-OXOTOTARA-2,8,11,13-TETRAENE
Authors: Matsumoto Takashi , Ohno Toru , Fujita Hitoshi , Fukui Kenji
Published: July 2006

For structural elucidation of shonanol, (±)-14-hydroxy-12-isopropyl-3-oxopodocarpa-1,8,11,13-tetraene (II), (±)-14-hydroxy-12-isopropyl-1-oxopodocarpa-2,8,11,13-tetraene (III), and (±)-12-hydroxy-1-oxototara-2,8,11,13-tetraene (IV) were synthesized. However, the synthetic II-IV were shown to be not identical with shonanol.
PHOTOCHEMICAL REACTION OF THE p-BENZOQUlNONES IN MICELLAR SYSTEM
Authors: Kano Koji , Matsuo Taku
Published: July 2006

The photochemical reaction of p-benzoquinone and duroquinone in the presence of the surfactants has been investigated in aerobic phosphate buffer (pH 6.8). The photoreaction of p-benzoquinone was accelerated by the addition of sodium laurate (Φ/Φ0 = 1.6) and sodium lauryl sulfate (Φ/Φ0 = 1.4). Polysorbate 80 did not affect (Φ/Φ0 = 1.0) and hexadecylethyldimethylammonium bromide markedly suppressed the photoreaction of p-benzoquinone (Φ/Φ0 = 0.56). Meanwhile, the photoreaction of duroquinone was slightly suppressed by the anionic and non-ionic surfactants and was completely inhibited by the cationic one. The acceleration of the photoreaction of p-benzoquinone by the anionic surfactants was ascribed to the formation of the p-benzoquinone–micelle complex as confirmed by means of NMR spectroscopy. The results of the micellar effects on p-benzoquinone photochemistry suggest the formation of a cationic species as an intermediate.
BEHAVIOR OF α-METHOXYCYCLOPROPYL RADICAL IN HUNSDIECKER REACTION
Authors: Ando Teiichi , Yamashita Akira , Matsumoto Masahiro , Ishihara Takashi , Yamanaka Hiroki
Published: July 2006

The Hunsdiecker reaction of trans-1-methoxy-2-methyl-3, 3-dichlorocyclopropanecarboxylic acid with bromine in carbon tetrachloride at 0°C and 77°C has been found to occur with substantial inversion of configuration, suggesting the low configurational stability of the α-methoxycyclopropyl radical as compared with the α-methoxyvinyl radical.
HYDROGEN BONDING OF PYRIDINE-CARBOXYLIC ACIDS IN SOLIDS
Authors: Takusagawa Fusao , Shimada Akira , Nishimoto Kichisuke
Published: July 2006

The nature of the hydrogen bonds in pyridine-carboxylic acids is studied theoretically. There is an interesting relationship between O···N and N···H distances in the systems. The relation can be reasonably explained by the consideration of the charge transfer interactions. The variation of the C–N–C bond angle of pyridine ring by a protonation can also be satisfactorily elucidated by INDO method.