bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxidation of Sulfite and Thiosulfate by the Cobalt(III) Complex of Dipicolinate in Aqueous Medium
Authors: Ali Mahammad , Saha Swapan K , Banerjee Pradyot
Published: July 2006

The oxidation of sulfite and thiosulfate by Co(dipic)2− (where H2dipic=2,6-pyridinedicarboxylic acid) was studied in aqueous medium. The reactions were carried out by varying reagent concentrations, pH, and ionic strength. For thiosulfate oxidation, the rate is zero order in complex and second order in thiosulfate. The reaction rates were found to increase with the acidity and the general rate law is expressed as kobs={k′0+k′1[H+]}[S2O32−]2 where k′0 and k′1 denote the acid independent and dependent paths respectively. The values of rate parameters are k′0=(2.87±0.20)×10−8 mol dm−3 s−1 and k′1=(0.57±0.02) mol−2 dm6 s−1 at 30°C. A plausible mechanism is suggested by considering the formation of an intermediate active species in the rate-determining step. The sulfite oxidation was, however, first order both in complex and reagent. An inverse dependence on [H+] was obtained for this reaction indicating a higher reactivity of the anionic species in solution. The general rate law is given by kobs=2(k1[SO2·H2O]+k2[HSO3−]+k3[SO32−]) and the evaluated second-order rate constants are: k1=(5.60±0.04)×10−5 mol−1 dm3 s−1, k2=(3.02±1.21)×10−3 mol−1 dm3 s−1 and k3=(4.91±0.05)×10−2 mol−1 dm3 s−1 at 60°C. The reactivity order SO32−>HSO3−>SO2·H2O has been explained successfully by considering the two isomeric structures for these species in solution. An overall rate law has been derived to interpret these results over the whole range of pH. The theoretical pH rate profile calculated from the different rate parameters shows an excellent agreement with the experimental one suggesting the validity of the proposed mechanism.
Gamma Radiolysis of Flavin Mononucleotide and Flavin-Adenine Dinucleotide in Aqueous Solution
Authors: Saha Abhijit , Mandal Parikshit Chandra , Bhattacharyya Sudhindra Nath
Published: July 2006

Flavin-adenine dinucleotide (FAD) and flavin mononucleotide (FMN) were irradiated with 60Co γ-ray and G-values for their decomposition under aerated, argon and nitrous oxide saturated conditions at pH 6.5 were determined by spectrophotometric, fluorescence and HPLC measurements. Among the water-borne radicals the hydroxyl radical (OH) was found to be responsible for causing permanent changes in FAD and FMN. The striking similarity between the difference spectra of irradiated FAD and FMN in N2O saturated conditions shows that the OH radicals attack at the isoalloxazine moiety. A plausible mechanism for the reaction of the OH radicals with the isoalloxazine moiety has been discussed. The rate constant for the reaction of isoalloxazine moiety of FAD with OH radicals was determined to be 4.7×109 dm3mol−1 s−1 by competition kinetic studies using glucose as the reference solute. From the kinetic consideration and G-values it is evident that ca. 50% of the OH radicals attack at the AMP (adenosine monophosphate) portion of FAD apart from isoalloxazine moiety. The attack at the AMP portion of FAD is supported by the observed phosphate release in the irradiated FAD solution. Effect of Fe3+ ion on the radiolysis of FAD and FMN was also studied.
Conductivity of Manganese(II) Sulfate in Aqueous Solution at Various Temperatures
Authors: Kubota Eiji , Takizawa Satoru , Kashiwagi Wataru , Yokoi Masatoki
Published: July 2006

The molar conductivity of manganese(II) sulfate, MnSC4, in aqueous solution was measured in a temperature range of 10–45°C. The acquired data were analyzed by the Quint-Viallard equation, and the resulting ion association constant, KA, was used in the Bjerrum equation to determine the contact ion size, RB. The limiting ionic molar conductivity λ0 (1/2 Mn2+) for the manganese ion at 15, 25, 35, and 45°C are 40.8, 53.1, 65.2, and 79.8 S cm2 mol−1, respectively. The resulting thermodynamic properties for the ion association reaction are: ΔG°298=−13.5 kJ mol−1, ΔH°=7.91 kJ mol−1, and ΔS°298=74.1 JK−1 mol−1.
Circular Dichroism Spectrum of Ci-trans(O)-[Co(C(S)-edma-d1)2]+ Containing Chiral Methylene Formed by Stereospecific Deuteration
Authors: Ama Tomoharu , Yasui Takaji , Hidaka Jinsai
Published: July 2006

C i-trans(O)-[Co(C(S)-edma-d1)2]+ was prepared by way of the stereospecific deuteration of the facially coordinated edma (ethylenediamine-N-acetate) in (−)543CD-C2-trans(O)-[Co(edma)2]+. The vicinal CD spectrum due to the C(S)-edma-d1 in the Ci-trans(O) complex was investigated in connection with the D→H exchange in the ligands, suggesting a two-step mechanism.
Diastereoselective Synthesis of 2,3-anti-5-Benzyloxy-2,4-dimethyl-1,3-pentanediols via Cyclic Hydroboration
Authors: Yokoyama Yasushi , Terada Yuji , Kawashima Hideyuki
Published: July 2006

The treatment of (2E,4S)- and (2Z,4S)-1-benzyloxy-5-ethenyloxy-2,4-dimethyl-2-pentene with borane both with and without a catalytic amount of Rh(Ph3P)3Cl gave 2,3-anti-3,4-anti-(2R,3R,4S)- and 2,3-anti-3,4-syn-(2R,3R,4R)-5-benzyloxy-2,4-dimethyl-1,3-pentanediols, respectively, with fair to good diastereoselectivity.
Halogenation Using Quaternary Ammonium Polyhalides. XXXI Halogenation of Thiophene Derivatives with Benzyltrimethylammonium Polyhalides
Authors: Okamoto Tsuyoshi , Kakinami Takaaki , Fujimoto Hiroshi , Kajigaeshi Shoji
Published: July 2006

The reactions of thiophene derivatives with benzyltrimethylammonium tetrachloroiodate, benzyltrimethylammonium tribromide, and benzyltrimethylammonium dichloroiodate in acetic acid or in acetic acid–zinc chloride under mild conditions gave chloro-, bromo-, and iodo-substituted thiophene derivatives, respectively, in satisfactory yields.
A New Calix[6]arene-Based Uranophile with Phosphonate Groups as Ligands
Authors: Nagasaki Takeshi , Arimura Takashi , Shinkai Seiji
Published: July 2006

A new calix[6]arene-based uranophile which has six phosphonomethyl groups on the upper rim was synthesized. This compound forms a 1 : 1 complex with uranyl ion (UO22+). The stability constant was estimated to be 1017.5 M−1, which is satisfactorily comparable with those for calix[6]arene-based uranophiles bearing OH or COOH groups on the lower rim.
The Formation of Two New Ring-Enlargement Products in the Lead Tetraacetate Oxidation of l-2(10)-Pinene
Authors: Matsubara Yoshiharu , Youzhu Yuan , Zhi Cheng , Takekuma Shin-ichi , Yamamoto Hiroshi
Published: July 2006

The oxidation of l-2(10)-pinene with lead tetraacetate in glacial acetic acid at 60°C afforded, besides fifteen known other products, (1S,6S)-7,7-dimethylbicyclo [4.1.1]octan-3-one (2) and (1S,6S)-2-one isomer (3), whose structures were established on the basis of their spectroscopic data. A possible reaction pathway for the formation of these new compounds 2 and 3 involving novel ring-enlargement is described.
Oxidative Cleavage of Chalcones by Electrochemically Generated Superoxide Ion (O2\divdot)
Authors: Singh Manorama , Singh Krishna Nand , Misra Ram Achal
Published: July 2006

Various chalcones were efficiently cleaved to carboxylic acid(s), in considerably high yield by the reaction with electrochemically generated superoxide ion (O2\divdot) at mercury cathode and molecular oxygen.
Mixed Adsorbed Film and Micelles of Sodium Taurocholate and Sodium Taurodeoxycholate
Authors: Wada Atsunori , Matubayasi Norihiro , Motomura Kinsi
Published: July 2006

The surface tension of an aqueous mixture of sodium taurocholate (NaTC) and sodium taurodeoxycholate (NaTDC) in the presence of 0.1 mol kg−1 sodium chloride was measured as a function of the total concentration and composition of the bile salts at 25°C. The result, processed by a thermodynamic treatment based on excess thermodynamic quantities, showed that NaTC and NaTDC are freely miscible in an adsorbed film, while mixing in a limited composition region of the micelle.
Thermal Decomposition of Ammonium Amidotriphosphate (NH4)4P3O9NH2·H2O
Authors: Takenaka Atsushi , Ooe Junichi , Motooka Itaru , Nariai Hiroyuki
Published: July 2006

Ammonium amidotriphosphate (NH4)4P3O9NH2·H2O was heated at 5 K min−1 up to 100, 145, 180, and 240 °C in four different atmospheres: in a stream of dry air, humid air, ammonia, and dry hydrogen chloride. The products were analyzed by HPLC-FIA, X-ray diffractometry, and IR spectrophotometry. A new phase of ammonium cyclo-triphosphate was observed at lower temperatures, except for in the ammonia atmosphere. Oligophosphates (chain length=4–12) were more abundant in samples heated to 145 and 180°C in hydrogen chloride. The cyclo-tri- and oligophosphates were most probably formed via a zwitterion form. When heated to 240°C, the samples were changed to ammonium polyphosphates. Elemental analyses for the sample heated to 240°C in dry air showed that the ammonium polyphosphates formed contained some phosphorus-nitrogen bonds. Isothermal experiments at 180°C in dry air indicated that the new phase of ammonium cyclo-triphosphate was converted completely to ammonium polyphosphates.
Association of Cycloalkanes with Cyclodextrins in Aqueous Medium
Authors: Osajima Tomonori , Deguchi Toshio , Sanemasa Isao
Published: July 2006

The complex formation of α-, β-, and γ-cyclodextrins (CyDs, hosts) with five cycloalkanes (guests), cyclo(pentane, hexane, heptane, octane, and decane), has been studied in aqueous media at 25°C by making use of the volatilization rate of guest molecules from the aqueous into gas phase. In the excess of the host, α-CyD forms both 1 : 1 and 2 : 1 (host: guest) complexes, while β- and γ-CyDs form 1 : 1 complexes with an exception that β-CyD forms a 2 : 1 complex with cylodecane. The 2 : 1 complex formation constants of α-CyD with cyclo(hexane, heptane, octane, and decane), particularly with cyclooctane, are extremely large compared with their 1 : 1 formation constants. The host–guest spatial fitting models are proposed.
A New Reduction of Some Carboxylic Esters with Sodium Borohydride and Zinc Chloride in the Presence of a Tertiary Amine
Authors: Yamakawa Tomio , Masaki Mitsuo , Nohira Hiroyuki
Published: July 2006

In the presence of a tertiary amine, sodium borohydride (NaBH4) combined with zinc chloride (ZnCl2) showed powerful reducing properties and carboxylic esters were smoothly reduced to their corresponding alcohols which were not obtained by reduction with NaBH4 and ZnCl2 alone. Tetrahydrofuran (THF) was an efficient solvent, and the effective molar ratio of the reducing agents, NaBH4 : ZnCl2 : tertiary amine, was 2 : 1 : 1. In particular, aminobenzoates such as anthranilic esters, were reduced to aminobenzyl alcohols with high yields without the addition of a tertiary amine. Further, it was also found that this combination reduced nitro, cyano, and amido groups to their corresponding amino groups.
Flash Photolytic Generation of a Dithio Carbocation from 1,3-Dithiolane Derivatives and Its Reaction with Nucleophiles
Authors: Okuyama Tadashi , Haga Naoki , Takane Shin-ya , Ueno Kenji , Fueno Takayuki
Published: July 2006

2-Phenyl-1,3-dithiolanylium ion is generated as a transient intermediate by flash photolysis of aqueous ethanol and acetonitrile solutions of 2-methoxy and other dithiolane derivatives with a xenon lamp. Decay of the absorption (342 nm) of the cation generated from the 2-methoxy derivative follows pseudo-first-order kinetics. Rate constants were measured for the reaction of the cation with various nucleophiles. Decay curves for the cations generated from 2-arylthio and 2-sulfonyl derivatives are steep and show second-order kinetic character owing to the recombination of the cation with the counter anions (thiolate and sulfinate).
Photochemistry of 2H-Azirine—Formation of Nitrile Ylide Evidenced by Laser Flash Photolysis and Pulse Radiolysis—
Authors: Naito Ikuo , Morihara Hideaki , Ishida Akito , Takamuku Setsuo , Isomura Kazuaki , Taniguchi Hiroshi
Published: July 2006

Laser flash photolysis of 3-(4-biphenylyl)-2H-azirine (AZ) was carried out in cyclohexane for the direct detection of a nitrile ylide (NY). Two kinds of transient species, triplet AZ (T1) and NY, have been measured. Decay rates of these species were determined to be 6.7×105 s−1 (T1) and 8×10 s−1 (NY). The rate constants for the reactions of NY toward acetone and acrylonitrile were determined to be 2.5×103 dm3 mol−1 s−1 and 2.3×106 dm3 mol−1 s−1, respectively. These results were supported by the results of pulse radiolysis of AZ in benzene and stational irradiations of AZ.
The Synthesis of Hyptol and Its C-15 Epimer from (+)-Dehydroabietic Acid
Authors: Matsumoto Takashi , Terao Hiromitsu , Wada Makoto , Imai Sachihiko
Published: July 2006

In order to elucidate the absolute configuration of C-15 in natural hyptol, methyl (15S)-12,16-dihydroxy-8,11,13-abietatrien-18-oate and its (15R)-epimer were transformed into (15S)-12,16-epoxy-11,14-dihydroxy-8,11,13-abietatrien-7-one (1a) and its (15R)-epimer (1b), respectively. The synthetic 1a w as identical to natural hyptol. Thus, the stereochemistry of C-15 in the natural compound was conclusively assigned as S-configuration.
H-Aggregate of a Long-Chain Crystal Violet Dye in Langmuir–Blodgett Films
Authors: Miyata Akio , Unuma Yutaka , Higashigaki Yoshiyuki
Published: July 2006

The molecular orientation and aggregate formation in Crystal Violet (CV) dye monomolecular layers have been investigated by means of polarized reflection and absorption spectral measurements at an incident angle of 60°. A relatively sharp absorption band at 2.04 eV and a broad band around 2.23 eV assignable to the J-dimer and the H-dimer, respectively, were observed in the optical measurement geometry with polarized light either parallel(p) or perpendicular(s) to the incident plane. A sharp band at 2.61 eV, assigned to the H-aggregate (tetramer), was detected by p-polarized spectral measurement, but not s-polarized measurement. The J- and H-dimers have horizontal transition moments and the H-aggregate has a vertical transition moment. The H-aggregate peak shifted from 2.53 eV (10 mN m−1) to 2.61 eV (40 mN m−1) with increasing surface pressure. This is due to an increase in the slip angle between the transition dipole moments and their center-to-center lines because the chromophoric planes become to be gradually oriented normal to the water surface. The behavior of these aggregates is interpreted in terms of the extended dipole model.
High-Resolution Solid-State Cross-Polarization Magic-Angle Spinning 13C NMR of Metal-Free Phthalocyanines
Authors: Enokida Toshio , Hirohashi Ryo , Morohashi Nobuo
Published: July 2006

The high-resolution solid-state cross-polarization magic-angle spinning 13C NMR spectra of α, β, τ and X-form metal-free phthalocyanines (H2pc) were investigated. Chemical shifts differed according to crystal forms. As a result of the temperature dependence of chemical shifts, we could observe the change in the spectra because of the inner protons.
Co-Intercalation of Tetrahydrofuran and Propylene Carbonate with Alkali Metals in β-ZrNCl Layer Structured Crystal
Authors: Ohashi Masao , Uyeoka Koji , Yamanaka Shoji , Hattori Makoto
Published: July 2006

Alkali metal intercalation compounds of β-ZrNCl were prepared by both chemical and electrochemical processes in tetrahydrofuran (THF) and propylene carbonate (PC), used as solvents. Among the six combinations of alkali metals (Li, Na, and K) with THF and PC, only the Na–THF system did not form a co-intercalation phase. In the other systems, the solvent molecules co-intercalated with alkali metals in mono- and double layer arrangements between the chloride layers of β-ZrNCl, the structures of which were estimated from one-dimensional electron distribution maps along the direction normal to the basal plane. The electrochemical characteristics of β-ZrNCl, used as the cathode of a lithium battery, were greatly influenced by the electrolyte solvent used. The co-intercalation mechanisms are discussed in terms of the energetics of the solvation of alkali metal ions with polar molecules and an expansion of the β-ZrNCl interlayers.
Theoretical Estimation of the Entropies of Solvation of Univalent Ions
Authors: Abe Takehiro
Published: July 2006

A simple theoretical expression for the entropies of solvation of univalent ions has been derived by using a modified Born equation and has been successfully applied to several ions in water and to the typical ions Rb+ and Cl− in various solvents.
Redox Properties for Pentacoordinated Manganese(III) Complexes with Bis(salicylideneamino)alkanes
Authors: Nakamura Masaaki , Miyanaka Yuri , Ohmura Yasuhiro , Sekine Satoko , Huang Hu , Kai Fumiaki
Published: July 2006

The oxidation potentials of Mn(III/IV) for pentacoordinated chloromanganese(III) complexes with bis(salicylideneamino)alkanes shifted cathodically in the presence of excess chloride ions in their solution. The formation of dichloromanganese(IV) complexes with Schiff bases was spectrophotometrically detected by addition of chloride and hydrogen ions to acetonitrile solutions of the corresponding chloromanganese(III) complexes under aerobic conditions.
Apparent Molal Volumes of Urea and Its Derivatives in Aqueous Alkali Chloride Solutions
Authors: Ogawa Toshio , Mizutani Kiyoshi , Ando Yukimi , Yasuda Motoo
Published: July 2006

The apparent molal volumes (φv) at 25°C have been measured for the following urea derivatives in aqueous alkali chloride solutions (from density measurements) using a digital densimeter: urea, methylurea, ethylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1-diethylurea, and 1,3-diethylurea. The limiting values (φv°) were obtained by a linear extrapolation using the least-squares method. A notable feature of the transfer volumes found in this study was that hydrophobic urea derivatives, such as dimethylureas and diethylureas, had negative values for transfer from water to lithium chloride solutions. For the remainder, however, all transfer volumes were positive.
Structural Study of Triazole Antifungals. II. Crystal and Molecular Structures of the Two Diastereoisomers (4R*,5R*)- and (4S*,5R*)-5-(2,4-Difluorophenyl)-4-methyl-5-[(1H-1,2,4-triazol-1-yl)methyl]-3-[4-(trifluoromethyl)benzoyl]oxazolidine
Authors: Hata Tadashi , Furukawa Youji , Konosu Toshiyuki , Oida Sadao
Published: July 2006

The title compounds were designed and synthesized as potential inhibitors of cytochrome P-450 14α-demethylase. The antifungal activity of (4R*,5R*)-isomer is markedly higher than that of (4S*,5R*)-isomer. The crystal structures of the two diastereoisomers were determined by X-ray diffraction technique. The final R indices of (4R*,5R*)- and (4S*,5R*)-isomers were 0.063 and 0.070 for 2840 and 2365 reflections, respectively. The different configuration at the 4-position in the oxazolidine ring causes the differences in the ring conformation and in some torsion angles. The three-dimensional structures of the two diastereoisomers are consequently different. Among the diastereoisomers and enantiomers, the (4R,5R)-enantiomer is superimposable on lanosterol, which is a substrate of cytochrome P-450 14α-demethylase, suggesting that the 4β-methyl group plays an important role in the antifungal activity.
Fragmentation of Energy-Selected Fluorobenzene Ion
Authors: Nishimura Toshihide , Meisels Gerry G , Niwa Yoshio
Published: July 2006

Dissociation of the fluorobenzene ion has been studied using threshold photoelectron–photoion coincidence (TPEPICO) mass spectrometry. The detailed breakdown curves were measured over internal energies from 0 to 9 eV. Asymmetric flight time distributions due to metastable dissociation were observed for the formations of C6H5+ and C4H3F+, and their absolute decay rate constants were derived from their flight time distributions. The information-theoretical approach has been employed for the analysis of kinetic energy release distribution (KERD). The results of surprisal analysis demonstrated that experimental KERDs are in good agreement with the predictions based on the statistical theory of mass spectra (QET). The heat of formation of C4H3F·+ has been estimated to be 222±2 kcal mol−1.
Chemical Analysis of Thortveitite from Oro, Mineyama-cho, Naka-gun, Kyoto Prefecture, Japan
Authors: Moriyasu Kazuhisa , Nishikawa Yasuharu
Published: July 2006

The geochemically interesting rare mineral, thortveitite, from Oro, Kyoto Prefecture was studied. Major constituents, scandium, yttrium, and lanthanoids, niobium, tantalum, aluminum, titanium, iron, calcium, and manganese were determined. The chemical analysis of the mineral assemblage gave Sc2O3 18.20, Y2O3 0.72, Σ Ln2O3 1.70, FeO 0.97, MnO 0.54, Nb2O5 trace, Ta2O5 9.96, Al2O3 3.02, CaO 1.72, TiO2 0.83, SiO2 58.31, and H2O 4.20; total 100.17%. This sample contained tantalite 11.47, anorthite 8.37, rutile 0.83, and quartz 37.91% in addition to thortveitite 37.40%. Scandium-tantalum substitution is suggested to occur similarly to yttrium-niobium substitution in earth acid minerals.
A Hydrogen Insertion Compound of Molybdenum Oxide Hydrate, H0.12–0.22MoO3·H2O, and Its Formation Process from Hydrogen Molybdenum Bronze, HxMoO3
Authors: Eda Kazuo , Sotani Noriyuki
Published: July 2006

Based on XRD and chemical analysis results, the hydrogen insertion compound of molybdenum oxide hydrate (H-hydrate) was suggested to be a genotypic compound of yellow molybdenum trioxide monohydrate, MoO3·H2O. H-hydrate was obtained in a hot HCl solution and in hot water from hydrogen molybdenum bronze, HxMoO3. The hydrogen bronze with x≤0.24 and the molybdenum species formed in the solution played a role in the formation of H-hydrate. In this process, a temporary dissolution of Mo5+ was observed at the beginning of the formation.
Structure and Homogeneous Chemical Equilibria of Lithium β-Diketonates in Dimethyl Sulfoxide
Authors: Araki Yoshinori , Iwase Akio , Kudo Setsuko , Suzuki Toshishige M , Yokoyama Toshiro
Published: July 2006

The structure and the homogeneous chemical equilibria of lithium β-diketonates (LiL), viz., Li(dbm), Li(bzac), and Li(acac), in dimethyl sulfoxide (DMSO) were studied by means of 13C NMR, IR spectral measurements, and rotating disk voltammetry, where dbm−, bzac−, and acac− indicate the enolate anions of dibenzoylmethane, benzoylacetone, and acetylacetone, respectively. It was found by the 13C NMR and IR spectral measurements that LiL existed mainly as Li(uni-L) in DMSO, where uni- means that the ligand coordinates to the metal as unidentate. Since it is known that LiL dissociates slightly into ions in DMSO, LiL is involved in the following homogeneous chemical equilibrium:

Li(uni-L)\ightleftharpoonsL++L−

Furthermore, the apparent dissociation constant (logKapp) of LiL was obtained by rotating disk voltammetry in DMSO containing 0.1 mol dm−3 tetrabutylammonium perchlorate (TBAP), i.e., Li(dbm): −3.0±0.1, Li(bzac): −2.7±0.1, and Li(acac): −2.0±0.1, respectively. It was noted that the homogeneous chemical equilibria shifted more to the right in 0.1 mol dm−3 TBAP–DMSO than in DMSO alone. The behavior can be explained mainly in terms of the interaction between the π-electron system of Li(uni-L) and the cations of TBAP.
Isomerization and Racemization of the Tris(4,4′-dimethyl-2,2′-bipyridine N,N′-dioxide)chromium(III) Complex
Authors: Kanno Hideaki , Yamamoto Junko , Murahashi Satoshi , Utsuno Shunji , Fujita Junnosuke
Published: July 2006

A new chromium(III) complex, [Cr(4,4′-Me2bpdo)3]3+ (4,4′-Me2bpdo=4,4′-dimethyl-2,2′-bipyridine N,N′-dioxide) was prepared and resolved into a pair of enantiomers by an SP-Sephadex column chromatographic method using an achiral eluting agent Na2SO4. Both perchlorate and nitrate of the complex were found to crystallize in the lel2·ob(Δ(λλδ), Λ(δδλ)), form. Upon dissolution in water, the complexes isomerized to the lel3(Δ(λλλ), Λ(δδδ)), form with a rapid change in absorption spectra, and then racemized (Δ\ightleftarrowsΛ) slowly. The rate constants at 35.0°C were 4.39×10−3 s−1 for the isomerization and 3.46×10−5 s−1 for the racemization. These inversion reactions including conformational change (δ\ightleftarrowsλ) and configurational change (Δ\ightleftarrowsΛ) are supposed to proceed by intramolecular mechanisms. The rates of isomerization and racemizatioin of the 4,4′-Me2bpdo complex are ca. two and ten times slower than those of [Cr(bpdo)3]3+ (bpdo=2,2′-bipyridine N,N′-dioxide), respectively.
Preparation and Characterization of Cobalt(III), Nickel(II), and Copper(I) Complexes Containing 5,8-Diphenyl-5,8-diphospha-2,11-dithiadodecane (L), CH3SCH2CH2P(C6H5)CH2CH2P(C6H5)CH2CH2SCH3, and Molecular Structure of [Ni(rac(P)-L)2](BF4)2
Authors: Kitagawa Tetsuji , Kita Masakazu , Kashiwabara Kazuo , Fujita Junnosuke
Published: July 2006

Δ-RR,Λ-SS-[Co(acac)2(rac(P)-L]+ and [Co(acac)2(meso(P)-L)]+ were obtained by reaction of [Co(acac)3] (acac=2,4-pentanedionate ion) with 5,8-diphenyl-5,8-diphospha-2,11-dithiadodecane (L) in 1 : 1 molar ratio in dichloromethane in the presence of active charcoal, no Δ-SS,Λ-RR isomer of the rac(P)-L complex being formed. Five-coordinate [Ni(rac(P)-L)2]2+ and [Ni(meso(P)-L)2]2+ were yielded by reaction of Ni(II) and L in 1 : 2 molar ratio in methanol, and the molecular structure of less soluble [Ni(rac(P)-L)2](BF4)2 was determined by X-ray analysis. Crystal data: monoclinic, space group P21⁄n, a=17.136(3), b=20.134(5), c=14.106(3) Å, β=93.30(2)°, V=4859(2) Å3, Z=4, R=0.089 for 8001 reflections. The Ni atom is surrounded square pyramidally by four P atoms in the basal plane and one S atom at the apical position with distances of the Ni–P: 2.214(2)–2.234(2) Å and the Ni–S: 2.603(2) Å. Both [Ni(rac(P)-L)2]2+ and [Ni(meso(P)-L)2]2+ in CH2Cl2 solutions exchange four –SCH3 groups at the apical positin on the NMR time scale. White [Cu(rac(P)-L)]BF4 was precipitated selectively by reaction of Cu(BF4)2·6H2O and L in 1 : 1 molar ratio in ethanol.
A Novel and Efficient Method for the Preparation of α-Hydroxyimino Carbonyl Compounds from α,β-Unsaturated Carbonyl Compounds with Butyl Nitrite and Phenylsilane Catalyzed by a Cobalt(II) Complex
Authors: Kato Koji , Mukaiyama Teruaki
Published: July 2006

Various α,β-unsaturated carbonyl compounds, such as α,β-unsaturated esters, α,β-unsaturated ketones, α,β-unsaturated nitriles, and α,β-unsaturated amides, were directly converted to the corresponding a-hydroxyimino carbonyl compounds in high yields on treatment with butyl nitrite and phenylsilane in the presence of a catalytic amount of N,N′-bis(2-ethoxycarbonyl-3-oxobutylidene)ethylenediaminatocobalt(II) complex under mild conditions.
Effects of Lateral Substituents on the Mesomorphic Properties of N-[4-(4-Methoxybenzoyloxy)benzylidene]aniline and Its Isomeric Compound
Authors: Hasegawa Hiroyuki , Matsunaga Yoshio , Miyajima Nobuhiko
Published: July 2006

The nematic phases exhibited by the title compounds carrying a hydroxyl or cyano group at the 2-position of the aniline moiety are thermally more stable than expected on the basis of the relationship between the nematic–isotropic transition temperature of the corresponding halogeno derivatives and the van der Waals volume of the substituents.
Conjugate Reduction of 2-Butene-1,4-diones with LiAlH4–SbCl3
Authors: Sayama Shinsei , Inamura Yutaka
Published: July 2006

The reagent LiAlH4–SbCl3 was found to be more effective for a conjugate reduction of 2-butene-1,4-diones in comparison with the reagent LiAlH4–other metal halides.
Thermodynamic Studies of Copper(II) Sulfate in Aqueous Mannitol from Electromotive Force Measurements
Authors: Blokhra Ratan L , Sharma Anil K
Published: July 2006

Electromotive force measurements of the cell Cu–Hg/CuSO4(m)/Hg2SO4(s)/Hg have been made at 288, 298, 308, and 318 K for mannitol composition X=5, 15, and 25% (w/w) in water. The standard emf values of the cell at different temperatures and at different composition of mannitol + water mixtures have been determined by an extrapolation method. These have been utilized to evaluate the mean activity coefficient of copper(II) sulfate. The standard free energy for the cell reaction, and the primary medium effects upon CuSO4 have been evaluated. The standard thermodynamic quantities for the process of transfer of CuSO4 from water to the mannitol solution have been calculated from the values of the standard potential. The transfer parameters have been split into the electrostatic and chemical contributions and the results have been explained in the light of ion–solvent interactions and structural contributions to solvents.
Anionic Surfactants with Divalent Counterions of Separate Electric Charge. III. Proton NMR Study
Authors: Moroi Yoshikiyo , Matuura Ryohei , Yonemitsu Tadashi
Published: July 2006

The proton NMR spectra of 1-tetradecanesulfonates whose cationic counterion, the 1,1′-polymethylenedipyridinium ion (with even-numbered methylene groups up to 14), is divalent with separate electric charge, were measured. From the chemical shifts the pyridine rings were found to move about in quite hydrophilic environment of micellar surface region, leading to a downfield shift of methylene groups next to head group of surfactant ion. The chemical shifts of methylene groups of micellized counterions with more than eight methylene groups are different from those of corresponding counterions in aqueous environment and are similar to those of methylene group in hydrophobic micellar interior. These results strongly support the previous conclusion that the polymethylene group with more than eight methylene groups folds and penetrates micellar interior in their micellized state.
Exothermic Reactions in C2 Hydrocarbon Flames
Authors: Fukutani Seishiro , Kunioshi Nílson , Sakaguchi Keizo , Jinno Hiroshi
Published: July 2006

Premixed stoichiometric flames of acetylene, ethylene, and ethane with air were investigated using a chemical scheme composed of eighty-two pairs of elementary reactions to illustrate the dependence of the propagation mechanisms of C2 hydrocarbon flames on the heat release distribution. The general role of heat release distribution through flames was depicted by means of an analytical treatment of the governing equations with the thermal properties of the gases being constant and the temperature profile given by an appropriate function of the position in the flame. It was found that the amount of heat released by chemical reactions at low-temperature regions of a flame is of fundamental importance for its propagation and that the main trigger of exothermic reactions at those zones is hydrogen atoms, which diffuses from the flame front; in the acetylene flame reactions consuming hydrogen atoms at the low-temperature region were found to yield all the heat released at that zone. Heat release distribution extended down to low-temperature regions was found to be able to lead to large burning velocities even though the amount of heat released at each position was small.
Correlations among One-Bond Deuterium Isotope Shifts in 13C NMR and C–H Stretching Frequencies in IR for Monosubstituted Methane Derivatives
Authors: Nakashima Yasuki , Takahashi Kensuke
Published: July 2006

The effects of one bond deuterium isotope on 13C NMR chemical shifts (1Δ) of the title compounds were found to be correlated with the corresponding C–H stretching frequencies(νCH) in IR spectroscopy, as follows: 1Δ(ppb)=−8.69 νCH(cm−1)+26500.
Acceleration of the Hydrogenation of 2-Octanone with an Alkali Salt of an Organic Acid
Authors: Osawa Tsutomu , Harada Tadao
Published: July 2006

The hydrogenation of 2-octanone over various types of nickel catalysts was found to be accelerated by the addition of small amounts of carboxylates of alkali metals such as Na, K, and Li.
A Convenient Synthesis of Monofluorobutene Derivatives
Authors: Matsuo Noritada , Kende Andrew S
Published: July 2006

(Z)-1,4-Dibromo-1,1,2-trifluoro-2-butene (2a) reacts regioselectively with sodium benzenesulfinate and triethyl phosphite respectively to yield the (Z)-isomers of 3,4,4-trifluoro-4-bromo-2-butenyl phenyl sulfone (3) and diethyl (Z)-4-bromo-3,4,4-trifluoro-2-butenylphosphonate (6). These could easily be transformed to a variety of polyfunctional monofluoroalkene derivatives.
Effect of Water Vapor on the Transformation of cyclo-Tetraphosphate
Authors: Nariai Hiroyuki , Motooka Itaru , Tsuhako Mitsutomo
Published: July 2006

The effect of water vapor on the process of transformation of sodium cyclo-tetraphosphate Na4P4O12(P4m) to sodium cyclo-triphosphate Na3P3O9(P3m) was investigated by means of DTA-TG, X-ray diffraction analysis, isothermal heating with an electric furnace, and HPLC. The transformation of P4m to P3m proceeded by a radical reaction via different reaction pathways in dry and humid air.
Soccerane Derivatives of Given Symmetries
Authors: Fujita Shinsaku
Published: July 2006

Symmetrical properties of soccerane and its derivatives are discussed in the light of subduction of coset representations (CRs). The 60 vertices of soccerane are equivalent and construct a single orbit governed by the CR, Ih(/Cs). This orbit is divided into several orbits in the respective derivative, where the mode of the division is controlled by the subduction. The number of derivatives with a given formula and a given subsymmetry is calculated in terms of unit subduced cycle indices, which are derived from the subduction.
Syntheses of Anionic Surfactants Having Two Polyfluoroalkyl Chains and Their Flocculation Ability for Dispersed Magnetite Particles in Water
Authors: Yoshino Norio , Komine Noboru , Suzuki Jun-ichi , Arima Yuki , Hirai Hidefumi
Published: July 2006

Four anionic surfactants having two polyfluoroalkyl chains in a molecule, sodium salt of bis(1H,1H,2H,2H-heptadecafluorodecyl) 2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, sodium salt of bis(1H,1H,9H-hexadecafruorononyl) 2-sulfosuccinate, H(CF2)8CH2OCOCH2CH(SO3Na)COOCH2(CF2)8H, sodium salt of bis(1H,1H,7H-dodecafluoroheptyl) 2-sulfosuccinate, H(CF2)6CH2OCOCH2CH(SO3Na)COOCH2(CF2)6H and sodium salt of bis(1H,1H,5H-octafluoropentyl) 2-sulfosuccinate, H(CF2)4CH2OCOCH2CH(SO3Na)COOCH2(CF2)4H, were prepared from maleic anhydride, the corresponding alcohols having a polyfluoroalkyl chain and sodium hydrogensulfite. The flocculation and redispersion abilities of these surfactants against dispersed magnetite particles in water have been examined in comparison with other four anionic surfactants having a single polyfluoroalkyl chain in a molecule; sodium pentadecafluorooctanoate, CF3(CF2)6COONa, sodium 9H-hexadecafluorononanoate, H(CF2)8COONa, sodium 7H-dodecafluoroheptanoate, H(CF2)6COONa, and sodium 5H-octafluoropentanoate, H(CF2)4COONa. These abilities were estimated by measurement of the contact angle against water using pelleted surface-modified magnetite. The abilities of the surfactants having two polyfluoroalkyl chains against flocculation-redispersion were superior to those of the surfactants having one polyfluoroalkyl chain. Especially, sodium salt of bis(1H,1H,2H,2H-heptadecafluorodecyl) 2-sulfosuccinate was the most effective surface active agent for these abilities.
Flash Vacuum Pyrolysis of 5-Diazodibenzo[ad]cycloheptene. Some Insights into Aromatic Carbene–Arylcarbene Rearrangement
Authors: Tomioka Hideo , Kobayashi Noriyuki
Published: July 2006

Flash vacuum pyrolysis of the title diazo compound gives 4H-cyclopenta[def]phenanthrene, which is interpreted as indicating that dibenzo[ad]cycloheptatrienylidene (13) undergoes the carbene–carbene rearrangement to generate 4-phenanthrylcarbene. The reactivities of 13 are compared with those of other benzoannulated cycloheptatrienylidenes and discussed in terms of the effect of the benzo ring to the activation energy for the rearrangement.
The Effect of Hydrogen Sulfide on Acridine Hydrodenitrogenation on a Sulfided NiMo/Al2O3 Catalyst
Authors: Nagai Masatoshi
Published: July 2006

The effect of hydrogen sulfide on acridine hydrodenitrogenation over a sulfided NiMo/Al2O3 catalyst at 280–380 °C and 10.1 MPa total pressure was studied. The result showed that the presence of H2S depressed the total C–N hydrogenolysis at a low PH2S/PH2 ratio of 1.1–79×10−5, but that it rarely affected the C–N hydrogenolysis at a ratio above 0.003.
Theoretical Foundation of Prochirality. Chirogenic Sites in an Enantiospheric Orbit
Authors: Fujita Shinsaku
Published: July 2006

Prochirality is one of the inherent properties of an enantiospheric orbit that is designated by a coset representation G(/Gi). Desymmetrization of the G(/Gi) orbit is discussed to present a new concept “H-chirogenic site”. The chirogenic site in the G(/Gi) orbit is capable of producing a chiral H-molecule under the influence of an appropriate chiral reagent. The condition for the existence of such a chirogenic site is discussed. A convenient method using a desymmetrization lattice is presented for determining chirogenic sites.
Formation of Halide Complexes of Methyl- and Inorganic Germaniun(IV) in Aqueous Hydrohalogenic Acid Solutions
Authors: Sohrin Yoshiki
Published: July 2006

The reaction of methyl- and inorganic germanium(IV) hydroxides ((CH3)nGe(OH)4−n; n=0,1,2, or 3) with halide ions (X=Cl−, Br−, or I−) to form halide complexes ((CH3)nGeX4−n) in aqueous acidic solution has been investigated by liquid–liquid extraction, solid–liquid distribution (ion exchange), and 1H NMR spectrometry. It has been found that methylgermanium moieties are hard Lewis acids similarly to inorganic germanium(IV), because the stability constant of the halide complexes decreases in the order Cl−>Br−>I−. The stability constant for an X− ion increases as the number of methyl groups attached to the germanium atom increases. The species of inorganic-, mono-methyl-, and dimethylgermanium are nonionic and have a tetrahedral structure in HX solution, and OH− ions attached to the germanium atom are stepwise substituted by X− ions with an increase in HX activity. Trimethylgermanium alone forms a cation, when the activity of HX is not sufficiently high. These facts suggest that the transfer of a negative charge from methyl groups to the central germanium atom lowers the stability of the bond between the germanium atom (hard acid) and an OH− ion (hard base).
Temperature- or Pressure-Induced Structure Changes of a Spin Crossover Fe(II) Complex; [Fe(bpy)2(NCS)2]
Authors: Konno Michiko , Mikami-Kido Mami
Published: July 2006

The crystal structures of polymorph II of diisothiocyanatobis(2,2′-bipyridine)iron(II), [Fe(bpy)2(NCS)2], in the high- (298 K) and low-spin states (175, 110 K) were determined by an X-ray diffraction method. The crystal is orthorhombic, space group Pcnb and Z=4 over the entire temperature range. At 298 K, a=13.2044 (6), b=16.4820 (7), c=10.1086 (7) Å, U=2200.0 (2) Å3, Dc=1.462 g cm−3 and at 110 K, a=12.9842 (9), b=16.1067 (12), c=9.8938 (8) Å, U=2069.1 (3) Å3, Dc=1.555 g cm−3. The structures were refined to R=0.047, 0.044, and 0.042 at 298, 175, and 110 K, respectively. The difference in the average Fe–N bond lengths between high- and low-spin states is 0.17 Å. The pressure dependence of the absorption spectra was also measured up to 8.5 GPa using a diamond anvil cell. These results indicate that with increasing pressure the high-spin state at 1 atm starts to change to the low-spin state at 0.3 GPa and that its low-spin state reverts again to the high-spin state at around 3.3 GPa.
High Thermodynamic Diastereoselection in the Equilibration of Acyclic γ-Alkoxy α-Amino Nitriles
Authors: Inaba Takashi , Fujita Makoto , Ogura Katsuyuki
Published: July 2006

An equilibrium between two diastereomers of an acyclic γ-alkoxy α-amino nitrile was attained in chloroform, and the major component is always its (R*, S*)-isomer with high diastereoselectivity.
Reaction of Cyanoguanidine with Formaldehyde. V. Properties of Cyanoguanidine–Formaldehyde Resin as a Coagulating Agent of Anionic Colloidal Particles
Authors: Shiba Ryuichi , Takahashi Miyuki , Ebisuno Toichi , Shindou Yoichi , Takimoto Michiaki
Published: July 2006

The coagulation of anionic colloidal particles by the cyanoguanidine (CG)–formaldehyde resin has been reported to be caused by an electrostatic interaction of the (diaminomethylene)urea (DU) cation with an anionic surface charge of particles. Our results show that neither DU·HCl nor di-hydrochlorides of N,N′-methylenebis [N′-(diaminomethylene)urea] (Bis-DU·2HCl), itself, nor the resinous products of DU·HCl or Bis-DU·2HCl with formaldehyde, are such effective coagulating agents as the CG–formaldehyde resin and are not explicable only in terms of the electrostatic interaction. Gel-permeation chromatograms of the resins have revealed that the coagulation efficiency increased in proportion to the increase of the fraction of components having higher molecular weight, suggesting that components having higher molecular weight play an important role in coagulation due to the CG–formaldehyde resin.
Effect of Anions on the Epoxidation of Styrenes with H2O2 in the Presence of Ammonium Heptamolybdate(VI)– Dioctyltin Oxide Catalysts
Authors: Inoue Masami , Nakayama Eiichi , Nakamura Yuuko , Rengakuji Seichi , Nishibe Keiichi
Published: July 2006

The epoxidation of styrene, α-methylstyrene, β-methylstyrene, p-chlorostyrene, and m-divinylbenzene with H2O2 in the presence of ammonium heptamolybdate(VI)–dioctyltin oxide catalysts in CHCl3–H2O was studied. The addition of neutral salts, such as NaNO3 or Na2SO4, to the catalyst system prevented the successive hydration of styrene oxide once formed. The presence of KCl or NaCl almost suppressed the oxidation, while no substantial effect was observed in NaClO4. The various effects of these anions were related to the results concerning the coordination of anions to Mo(VI)-ions.
Direct Synthesis of Trimethoxysilane from Methanol and Hydrogen-Treated Silicon Using Copper(II) Chloride as a Catalyst
Authors: Suzuki Eiichi , Kamata Takatsugu , Ono Yoshio
Published: July 2006

When silicon, on which copper(II) chloride was supported, was pretreated under a hydrogen stream at 533 K and brought in contact with methanol at 533 K, trimethoxysilane was formed with an 89% selectivity and a complete silicon conversion in 5.5 h. Pits were formed on the silicon surface, and grew with increasing silicon conversion.
Ab Initio Study of Pyridyl Cations, Anions, and Radicals
Authors: Kikuchi Osamu , Hondo Yuji , Yokoyama Yukihiro , Morihashi Kenji , Nakayama Mitsunobu
Published: July 2006

Ab initio calculations were carried out for the 2-, 3-, and 4-pyridyl cations, anions, and radicals in order to examine their molecular structures and relative energies among three isomers. The 4-31G//3-21G calculations have predicted that 2-pyridyl cation, 4-pyridyl anion, and 2-pyridyl radical are most stable among the isomers.
Graph-Theoretical Analysis of the Cyclic Bicalicene Conjugated Systems
Authors: Aihara Jun-ichi
Published: July 2006

The so-called cyclic bicalicene is aromatic although it can be regarded as a perturbed [16]annulene. Graph-theoretical analysis shows that the aromaticity of this molecule arises primarily from three- and five-membered circuits and their combinations. The peripheral sixteenmembered circuit presumably destabilizes the conjugated system to a very slight extent.
Determination of Methane Concentration in Air Extracted from Antarctic Ice Core Samples
Authors: Tohjima Yasunori , Tominaga Takeshi , Makide Yoshihiro , Fujii Yoshiyuki
Published: July 2006

A convenient method was developed for detrmination of methane concentration in old air trapped in Antarctic ice core samples. The air was extracted with a stainless steel bellows pump after quick refreezing of melted ice samples and the methane was measured with a gas chromatograph with an FID. The averaged methane concentration in the Mizuho ice core at a depth of 330 m (ca. 3600 BP, 11 samples) was 750±20 ppbv.
Preparation of 3,3-Bis(phosphoryl)cyclopropenes
Authors: Yoshida Hiroshi , Aoyama Masanori , Utsumi Fumitaka , Ogata Tsuyoshi , Matsumoto Kiyoshi
Published: July 2006

The reaction of 1,2-diphenyl- and 1-methyl-2-phenyl-3,3-dichloro- or dibromocyclopropenes with trialkyl phosphites, dialkyl phenylphosphonites, and alkyl diphenylphosphinites afforded cyclopropenes with 3,3-diorganophosphorous substituents in moderate yields via double Arbuzov type reactions.
Synthesis of (E)- and (Z)-2,3-Bis(trifluoromethyl)allyl Alcohols by γ-Ray Irradiation of Hexafluoro-2-butyne with Alcohols and Some Reactions
Authors: Nishida Masakazu , Hayakawa Yoshio , Matsui Masaki , Shibata Katsuyoshi , Muramatsu Hiroshige
Published: July 2006

Radiation-induced addition reaction of alcohols to hexafluoro-2-butyne provided (E)- and (Z)-2,3-bis(trifluoromethyl)allyl alcohols, which were dehydrated to afford 1,2-bis(trifluoromethyl)-1,3-butadienes. Thermal cyclization of 3-methyl-1,2-bis(trifluoromethyl)-1,3-butadiene afforded 1-methyl-2,3-bis(trifluoromethyl)clobutene.
Mass Transfer and Product-Selectivity in Electroreduction of p-Methylbenzaldehyde
Authors: Cheng Po-Chung , Nonaka Tsutomu
Published: July 2006

Mass transfer coefficients estimated from the formation ratio of the hydrodimeric to hydromonomeric products in electroreduction of p-methylbenzaldehyde in parallel plate electrode–flow cell and rotating cylinder electrode–beaker cell systems were shown in good agreement (less than 8% difference) with those obtained by ordinary current–potential and concentration–time methods.
Extended X-Ray Absorption Fine Structure Studies on Local Structure in Amorphous LaNi5.0 Films
Authors: Suenobu Tomoyoshi , Sakaguchi Hiroki , Tsuji Takaharu , Kanai Hiroyoshi , Yoshida Satohiro , Adachi Gin-ya
Published: July 2006

Analyses of the local structure around La and Ni atoms in amorphous LaNi5.0 films have been performed using the extended X-ray absorption fine structure (EXAFS), and the effect of the structure on the difference of hydrogen absorption characteristics between the amorphous and crystalline LaNi5.0 has been elucidated. The lengthening of interatomic distances for the Ni–Ni and La–Ni pairs, respectively, was observed for the amorphous samples in comparison with the crystalline ones. A part of the hydrogen sites existed in the crystalline LaNi5.0 was distorted in the amorphous one. Since the hydrogen atoms appear to be difficult to enter these sites distorted, the hydrogen content in the amorphous LaNi5 is smaller than that in the crystalline one.
Reactions of 1,1-Disubstituted Alkenes with Acetoacetamides and Molecular Oxygen in the Presence of Manganese(III) Acetate
Authors: Qian Chang-Yi , Nishino Hiroshi , Kurosawa Kazu
Published: July 2006

The reactions of 1,1-disubstituted ethenes with acetoacetamide or N-substituted acetoacetamides, and molecular oxygen in the presence of manganese(III) acetate gave a mixture of c-4- and t-4-carbamoyl-3-methyl-1,2-dioxan-r-3-ols in good yields. Effects of substituents in the alkenes as well as in the carbamoyl group in the acetoacetamides were observed. Stereochemistry and the reactivity of the 4-carbamoyl-3-methyl-1,2-dioxan-3-ols are discussed.
Selective Mono- and Bis(alkoxycarbonylation)s of Olefins Catalyzed by Palladium in the Presence of Cu(I) or Cu(II) Chloride under Remarkably Mild Conditions. Application to the Synthesis of γ-Butyrolactone Derivatives
Authors: Toda Shiho , Miyamoto Masanori , Kinoshita Hideki , Inomata Katsuhiko
Published: July 2006

Palladium-catalyzed mono- and bis(alkoxycarbonylation)s of olefins were controlled by the use of copper(II) and copper(1) chloride, respectively, in alcohol under normal pressure of carbon monoxide and oxygen at room temperature without any other additives. 3-Buten-1-ols gave the corresponding γ-butyrolactones and 2-oxotetrahydrofuran-3-acetic acid esters, respectively, in high yields.