bluuebunny/crossref_metadata_2025 huggingface dataset:
The Contraction of Water in the Hydration Shell
Authors: Shimizu Kiyoshi
Published: July 2006

In the aqueous solutions of some sulfates, the contraction of water molecules in a hydration shell and the hydration number were estimated by using the data of the limiting equivalent conductance of the ion and the partial molal volume of electrolytes at an infinite dilution.
A Vapor–Liquid Equilibrium Still Suitable for Small Amounts of Samples
Authors: Takagi Sadao
Published: July 2006

Details are described for the apparatus and procedures for the accurate measurement of vapor–liquid equilibria by use of small amounts of samples. The new recirculation still described is a modification of the Brown’s still (Aust. J. Sci. Res., A,  5, 530 (1952)) and its total amount of operating charge is ca. 53 cm3, of which each 7 cm3 is in the vapor- and liquid-sample traps and ca. 23 cm3 is in the boiler. A method of determining an optimum value of the heating current of the boiler is described. Partial condensation of the vapor and entrainment of the liquid phase into the vapor were eliminated. Some results obtained for the system hexane+chlorobenzene at 338.15 K agreed with the thermodynamically consistent values of Brown, showing the reliability of this still operating with the samples having relative volatilities up to 13. The construction of a thermostatted sample vessel without vapor space for a Pulfrich refractometer is also illustrated which is suitable for small quantity of volatile or hygroscopic solution.
35Cl-NQR of Some Chlorocarbons and Oxochlorocarbons with a Small Ring
Authors: Mano Koichi , Matsukura Takefumi , Fujino Akira
Published: July 2006

35Cl-NQR of two chlorocarbons and six oxochlorocarbons, all having a small ring, were measured in the temperature range 77–300 K. The NQR line groups for the allylic and vinylic chlorine atoms appear separately in the five-membered ring compounds, whereas they are concentrated in a rather narrow region near 38 MHz in the four-membered ones. Perchlorocyclopropene possesses at least three crystal modifications at 77 K, the most stable one of which has only two lines in the temperature range examined. The line assignments, and the hyperconjugative effect in some of them, are discussed with reference to the CNDO/2 MO calculation data.
Disintegration of Sulfonated Poly(1,4-piperazinediylterephthaloyl) Microcapsules by 1-Dodecylpyridinium Chloride
Authors: Suzuki Shiro , Nakamura Takashi , Kondo Tamotsu
Published: July 2006

Partially sulfonated poly(1,4-piperazinediylterephthaloyl)(SPP) microcapsules were found to undergo disintegration by the action of dodecylpyridinium ions when the surfactant cation concentration exceeded a certain value which was dependent on pH of the medium. At their lower concentrations, dodecylpyridinium ions interacted with negatively charged SPP microcapsules to produce aggregation of the latter. A polyelectrolyte-type viscosity behavior was observed with the complex formed between SPP and dodecylpyridinium ions in the disintegration process of the microcapsules. Crosslinking of the terminal amino groups of SPP microcapsules prevented disintegration from taking place.
Anodic Oxidation of 2-Aminofluorene at a Platinum Electrode in Acetonitrile Solutions
Authors: Yasukouchi Kazuo , Taniguchi Isao , Yamaguchi Hiroko , Miyaguchi Katsuji , Horie Koji
Published: July 2006

Anodic oxidation of 2-aminofluorene in acetonitrile solutions at a Pt electrode was investigated by using electrochemical techniques and by preparative-scale electrolyses. The cyclic voltammogram of 2-aminofluorene exhibited two anodic waves, which had peak potentials at 0.45 V (Ia) and 1.15 V (IIa) vs. Ag/0.01 M AgClO4. Wave IIa was due to oxidation of protonated 2-aminofluorene. In the voltammogram of repetitive sweeps, another redox couple (IIIa/IIIc) was observed at 0.13 V for IIIa and 0.06 V for IIIc, respectively. This indicates that at wave Ia, a species which is more easily oxidized than 2-aminofluorene was produced by follow-up chemical steps. By controlled-potential electrolysis at 0.5 V of a 2-aminofluorene solution containing pyridine as a prpton acceptor, a dark green product, 3-(2-fluorenylimino)-2,3-dihydro-2-fluorenimine (5) (or 1-(2-fluorenylimino)-1,2-dihydro-1-fluorenimine (5′)), precipitated as the main product in more than 70% yield. The oxidation pathway of 2-aminofluorene (Eqs. 1—4) has been proposed on the bases of the following results: (i) The apparent n-value was 1.95, (ii) two protons/molecule of 2-aminofluorene were released in the follow-up chemical steps, and (iii) the peak potential for oxidation of 2′-amino-2,3′-difluorenylamine (3) (or 2-amino-1,2′-difluorenylamine (3′)) was in good agreement with that of wave IIIa, and the anodic oxidation of 3 (or 3′) gave the same product as that obtained by oxidation of 2-aminofluorene.
Kinetics of the Formation and Transformation of Alkoxy-derived Calcium Metasilicate
Authors: Yamaguchi Osamu , Kamata Muneaki , Shimizu Kiyoshi
Published: July 2006

Wollastonite(β-CaSiO3) was formed directly from the mixed powder prepared by simultaneous hydrolysis of calcium and silicon alkoxides. Crystallization isotherms were described by the Avrami equation ln(1−α)=−ktn with n=3 and the activation energy was determined as 284.5 kJ/mol. The kinetics of transformation of β- into α-CaSiO3 was best interpreted by the contracting cube equation 1−(1−α)1⁄3=kt. The value of the activation energy was 983.2 kj/mol.
Syntheses of Alkylphosphonic Esters by the Reactions of Aliphatic Thiones with Trialkyl Phosphites
Authors: Kawase Tokuzo , Yoneda Shigeo , Yoshida Zen-ichi
Published: July 2006

Aliphatic thiones were found to react with trialkyl phosphites to give (alkylthio)- and/or mercapto-alkylphosphonic esters. The reaction is interpreted in terms of the carbophilic attack with trialkyl phosphites at the carbon atom of the thiocarbonyl group, and the subsequent migration mechanism via the betaine intermediate.
Replacement of Methoxyl Group on the Grignard Reaction of N-(o-Methoxybenzylidene)aniline
Authors: \={O}kubo Masao , Ueda Sonoko
Published: July 2006

The methoxyl group of the title imine was replaced by the phenyl group on treatment with PhMgBr, the same group of N-benzylidene-o-anisidine remaining. The result was discussed on the basis of radical chain mechanism involving the initial electron-transfer.
Syntheses of Cationic Mononucleotide Analogs and Their Interaction with Polynucleotide and Polynucleotide Analogs
Authors: Shimidzu Takeo , Murakami Akira , Yamana Kazushige , Konishi Yoshiyuki
Published: July 2006

Cationic mononucleotide analogs were synthesized through a quaternization reaction of N-halogenoethylated derivatives of nucleic acid bases or 5′-halogeno-5′-deoxynucleoside. When they interacted with polynucleotide and polynucleotide analogs with negative charges, base-base interactions were observed. The interactions between complementary bases were stronger than the others. It is suggested that an anionic field originating from the polynucleotide or polynucleotide analog contributes to the interaction of complementary bases.
Enantioface-differentiating Reactions Using (2S,2′S)-2-Hydroxymethyl-1-[(1-alkyl-2-pyrrolidinyl)methyl]pyrrolidines as Chiral Ligands. Addition of Lithium Derivatives of Methyl Phenyl Sulfide, Acetonitrile, N-Nitrosodimethylamine, and 2-Methylthiothiazoline to Aldehydes
Authors: Soai Kenso , Mukaiyama Teruaki
Published: July 2006

Optically active oxiranes, β-hydroxy nitrile, β-Hiydroxy N-nitrosoamine, and thiirane were obtained (up to 72% optical purity) by the enantioface-differentiating addition of lithium derivatives of methyl phenyl sulfide, acetonitrile, N-nitrosodimethylamine, and 2-methylthiothiazoline to aldehydes using (2S,2′S)-2-hydroxymethyl-1-[(1-alkyl-2-pyrrolidinyl)methyl]pyrrolidines (1a–f) as chiral ligands. Optical purity of the products depended greatly on the reaction medium (dimethoxymethane or dimethyl ether gave the best results) and the structure of pyrrolidine moieties of 1a–f.)
F-Propene-Dialkylamine Reaction Products as Fluorinating Agents
Authors: Takaoka Akio , Iwakiri Hiroshi , Ishikawa Nobuo
Published: July 2006

The reaction products of F-propene and dialkylamines, mixtures of α,α-difluoroalkylamine and α-fluoro enamine, were found to be useful fluorinating agents for alcohols and carboxylic acids. These reagents were superior to the adduct of chlorotrifluoroethene and diethylamine, the so-called Yarovenko reagent, for their readier preparation and higher stability.
Synthesis of cis-Aryl Cyclopropyl Sulfones
Authors: Balaji T , Reddy D Bhaskar
Published: July 2006

Some new cis-1-(arylsulfonyl)-2-phenylcyclopropanes have been synthesized by the addition of arylthiocarbenes to styrene in presence of excess potassium t-butoxide at low temperatures. The (arylthio)cyclopropanes thus obtained are subsequently oxidized with 30% hydrogen peroxide in acetic acid to corresponding sulfones. The IR and PMR spectra of all these compounds were recorded. Their IR spectra displayed bands in the region 1033–1008 cm−1 which are considered to be the most characteristic of the cyclopropane ring. They have also exhibited bands in the region 850–820 cm−1 characteristic of cis-configuration. The PMR spectra gave complex multiplets in the region 1.4–3.1 ppm. A study of these chemical shifts for ring protons and other substituents reveals that all the substituents tend to cause protons cis-to them to appear at higher fields than those trans-to them. Thus the differences of the chemical shifts can be used as a criterion to distinguish between cis-and trans-1-(arylsulfonyl)-2-phenylcyclopropanes.
Resonance Energy Stabilization in Crystalline Ion Radical Salts
Authors: Iida Yôichi
Published: July 2006

In solid ion radical salts, the ion radical molecules form a segregated stacking into columns, and the charge-transfer interaction occurs between ion radicals. The resonance energy stabilization due to the charge-transfer interaction was estimated for non-alternant one-dimensional system of solid ion radical salts.
Synthesis and Magnetism of Cobalt(II)–Manganese(II)–Cobalt(II) Trinuclear Complexes with N,N′-Disalicylidenealkanediamines
Authors: Kasempimolporn Visit , Okawa Hisashi , Kida Sigeo
Published: July 2006

Cobalt(II)–manganese(II)–cobalt(II) trinuclear complexes were synthesized by reacting N,N′-disalicylidenealkanediaminatocobalt(II) and manganese(II) halide in a 2:1 mole ratio. Cryomagnetic measurements indicated an antiferromagnetic spin-exchange interaction operating between the low-spin cobalt (II) and the high-spin manganese(II) ions, exchange integrals being estimated at −8–−12 cm−1.
Nucleophilic Substitution on Dialkoxy Bisulfides. II. Reactions with Hydrazine Derivatives
Authors: Kagami Hiroaki , Motoki Shinichi
Published: July 2006

Diethoxy disulfide (1) reacted with arylhydrazines to give arylbenzenes, diaryl sulfides, and aryl ethoxy tetrasulfides. The reaction of 1 with hydrazobenzenes gave azobenzenes in quantitative yields. The treatment of 1 with 1,5-diphenylthiocarbonohydrazide or 1,5-diarylthiocarbazones afforded 2,3-diaryltetrazolium-5-thiolates.
Photochemical Ethoxycarbonylmethylation of Anisole with Ethyl Chloroacetate in the Presence of Zinc Chloride
Authors: Izawa Yasuji , Tomioka Hideo , Kutsuna Masato , Toyama Yasuo
Published: July 2006

Irradiation of ethyl acetate solution of anisole and ethyl chloroacetate in the presence of ZnCl2 gave ethyl o-, m-, and p-methoxyphenylacetates (3) (28.6–48%). The similar ethoxycarbonylmethylation in anisole–ethyl acetate (9:1) resulted in higher yields (80–81%) of 3. The results on the positional and substrate selectivities imply that ZnCl2-participated attacking species would play an important role in the present ethoxycarbonylmethylation.
The BF3 Catalyzed Decomposition of Diazo Compounds in the Presence of Carbonyl Compounds
Authors: Ibata Toshikazu , Miyauchi Kazuo , Nakata Seiji
Published: July 2006

The BF3 catalyzed decomposition of diazo ompounds such as α-diazoacetophenones, ethyl diazoace-tate, and diphenyldiazomethane in the presence of cyclic β-diketones gave the corresponding enol ether. Used as a substrate, cyclohexanone gave the ring expanded homologation product.
Reaction of N,N-Dialkylanilines with Palladium(II) Compounds
Authors: Sakakibara Tsutomu , Dogomori Yoko , Tsuzuki Yuichiro
Published: July 2006

The reaction of N,N-dialkylaniline with palladium(II) acetate or di-μ-acetato-bis[α-(dimethylamino)-o-tolyl]dipalladium (B) gave 4,4′-bis(dialkylamino)diphenylmethane as a major product. It was elucidated that the origin of –CH2– in the product might be methyl group of palladium acetate and the primary reaction product might be N,N-dialkyltoluidine. The absorption spectra of the initial reaction mixture of N,N-dimethylaniline with B in acetic acid at room temperature showed the absorption maximum at 470 nm and at 750 nm. The latter peak was tentatively assigned to N,N-dimethylaniline radical cation-palladium (I) acetate complex, which was suggested as a key-intermediate for the formation of diarylmethanes.
The Mechanism of the TEA CO2 Laser-induced Reaction of 1,1-Dichloroethane
Authors: Nagai Keiichi , Katayama Mikio
Published: July 2006

In a TEA CO2 laser-induced reaction of 1,1-dichloroethane, the relative quantities of the products, C2H2 and ClHC=CH2, were found to vary with the laser wavelength, indicating that the C2H2 molecules are produced by two processes, directly and indirectly from Cl2HC–CH3 within the duration of a single laser pulse.
The Effect of Halo Ligand on the Rate of Hydrogenation of Coordinated Olefin in Dihydrido-olefin Complexes RhXH2(ol) (PPh3)2 (X=Cl, Br, I)
Authors: Ohtani Yoshimi , Yamagishi Akihiko , Fujimoto Masatoshi
Published: July 2006

The formation constant of RhXH2(ol)(PPh3)2 (ol=acrylonitrile or styrene, X=Cl, Br, or I) and the rate of hydrogenation of coordinated olefin in RhXH2(ol)(PPh3)2 were determined. The effects of halo ligand on the equilibrium and rate constants showed a different trend for the two olefin complexes.
Synthesis of 2,5-Diphenylbicyclo[4.2.0]octa-2,4-diene. Exclusive Existence in the Bicyclic Form and a Correction of the Reported Structure of 2,5-Diphenyl-1,3,5-cyclooctatriene
Authors: Oda Masaji , Kanao Yoshinori
Published: July 2006

2,5-Diphenylbicyclo[4.2.0]octa-2,4-diene has been found to exist exclusively in the bicyclic form, giving rise to questioning the reported structure of 2,5-diphenyl-1,3,5-cyclooctatriene. The structure of 1,4-diphenyl-1,3,6-cyclooctatriene is proposed for the compound.
Flux Growth of Double Oxide Crystals of Tantalum and Rare-earth Elements
Authors: Yamasaki Yuichi , Sugitani Yoshinori
Published: July 2006

Crystals of GdTaO4, DyTaO4, and ErTaO4, and those of Gd3TaO7, Y3TaO7 and Er3TaO7 have been grown by PbF2–PbO flux. Solid solution crystals of YTaO4 and YNbO4 have been obtained for the starting composition of YTaxNb1−xO4(x<0.5).
The Collection of Uranium from Sea Water with Hydrous Metal Oxide. II. The Mechanism of Uranium Adsorption on Hydrous Titanium(IV) Oxide
Authors: Yamashita Hisao , Ozawa Yoshihiro , Nakajima Fumito , Murata Toshifumi
Published: July 2006

The mechanism of uranium adsorption from sea water by hydrous titanium(IV) oxide was investigated. The uranium adsorption experiments were conducted using a solution containing NaCl, NaHCO3, and uranium. Thermochemical calculation showed that the tris(carbonato)dioxouranate(VI) ion [UO2(CO3)3]4− found in sea water existed in the solution at pH 8 and 25 °C. The uranium uptake varied with the pH of the solution, exhibiting a minimum value at pH 8. The enthalpy change, ΔH, and the activation energy, E, of the uranium adsorption were found to be 23.6 kJ mol−1 and 52.7 kJ mol−1 respectively. The analysis of carbonate in the adsorbent showed that the carbonate ion in [UO2(CO3)3]4− was released into the solution during the uranium adsorption. On the basis of the present experimental results, the mechanism of uranium adsorption was discussed.
The Crystal Structure of (Acetylacetonato)bis(diethylamine)palladium(II) Acetylacetonate at −170°C
Authors: Kotake Shoji , Sei Tsuyoshi , Miki Kunio , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The crystal structure of [{Pd(acac)(NHEt2)2}+(acac)−] at −170°C was determined by means of X-ray diffraction. The crystal belongs to monoclinic system: a=13.905(3), b=12.901(4), c=12.205(3) Å, β=96.28(2)°, space group I2/c with Z=4. The structure was established by the heavy atom method and refined anisotropically by the least-squares procedure; R=0.044 for 1558 non-zero reflections. Both the {Pd(acac)(NHEt2)2}+ cation and (acac)− anion lie on the crystallographic two-fold axis. The cation and anion lying on the same two-fold axis are bound together by two hydrogen bonds [N–H···O(2)=N′–H′···O(2′)=2.871(4) Å] to form an ion-pair. Two ion-pairs mutually related by the crystallographic center of symmetry make a packing unit of the crystal.
Halogenotriphenyltin(IV) Adducts of Tetrakis(t-butyl isocyanide)rhodium(I) Perchlorate. Preparation and Kinetics
Authors: Kuwae Ryosho , Tanaka Toshio
Published: July 2006

[Rh(t-BuNC)4]ClO4 undergoes oxidative addition reactions with Ph3SnX (X=Cl, Br) to give cis-[Rh-(Ph3Sn)X(t-BuNC)4]ClO4. The adducts partly dissociate in solution to exist as an equilibrium mixture with the Rh(I) substrate and the addendum. Kinetics of the equilibrium reactions in three different organic solvents were studied spectrophotometrically under pseudo-first-order conditions with excess Ph3SnX. Rate constants for the forward reaction (kf) are strongly dependent on the solvent polarity; kf increases in the order of 1,2-dichloroethane<acetone<acetonitrile, whereas those for the backward reaction are little dependent on the solvents. Activation parameters also were obtained for the X=Cl system in acetonitrile; ΔS\eweq for the forward reaction is −99.2 J mol−1 K−1, while that for the backward reaction is +24.9 J mol−1 K−1. These results indicate that the addition reactions proceed via a three-center transition state formed by the nucleophilic attack of the Rh(I) ion to the tin atom.
Chemical Studies on Tuberactinomycin. XVII. Synthesis of threo-γ-Hydroxy-l-β-lysine, Constituent Amino Acid of Tuberactinomycin A and N
Authors: Teshima Tadashi , Ando Toshihiko , Shiba Tetsuo
Published: July 2006

threo-γ-Hydroxy-l-β-lysine which is a constituent amino acid of antibiotics tuberactinomycin A and N, was synthesized from threo-β-hydroxy-l-ornithine derivative by the Arndt-Eistert reaction. The synthetic amino acid was identical with the natural sample in all respects. Furthermore, a route was established to prepare a protected γ-hydroxy-β-lysine derivative useful for the peptide synthesis.
Synthesis of 3-Carbamoyl-4-[(β-d-ribofuranosyl)methyl]pyrazole, a Pyrazole Homo-C-nucleoside
Authors: Sato Tsuneo , Noyori Ryoji
Published: July 2006

A facile, stereocontrolled synthesis of the title pyrazole homo-C-nucleoside is described.
The Molecular Structure of 1-Phenoxy-1,2,2a,8b-tetrahydrocyclobuta[α]naphthalene-8b-carbonitrile
Authors: Matsuura Hideaki , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The molecular structure of the sole photocycloaddition product of α-naphthonitrile with phenyl vinyl ether, C19H15ON was determined by means of X-ray diffraction. The crystals are monoclinic, space group P21/c, unit-cell dimensions are a=11.563(2), b=9.826(1), c=14.324(2) Å, β=113.46(1)°, Z=4. The structure was solved by the direct method, the final R value being 0,042 for 2022 non-zero reflections. The molecule has an endo-configuration, and the cyclobutane ring is puckered.
Infrared and ESR Spectra of Reaction Intermediates Formed from 1,1-Diphenylethylene Adsorbed on Oxides
Authors: Tani Noriko , Kawamori Asako , Yamada Haruka
Published: July 2006

When 1,1-diphenylethylene (DPE) was adsorbed on porous Vycor glass (PVG) or silica–alumina, some unstable reaction intermediates, blue, green, and yellow species, were formed. The blue species produced on the silica–alumina showed a characteristic band at 1525 cm−1, assigned to the shifted C=C stretching band, which disappeared in the green and yellow samples; it also showed an ESR signal. This indicates that the unstable blue species is probably a cation radical (Remark: Graphics omitted.). The infrared spectra of the green and yellow species on the silica–alumina showed new bands, ascribed to the –CH3 and –CH2– vibrations, which were in good agreement with the resonance Raman bands of the carbonium ions formed on the PVG. The green and yellow intermediates, therefore, should be two kinds of carbonium ions. The structures, formation mechanisms, and surface coverages of these intermediates are discussed.
The Modification of Tryptophyl Residues during the Acidolytic Cleavage of Boc-groups. I. Studies with Boc-Tryptophan
Authors: Masui Yoshihiro , Chino Naoyoshi , Sakakibara Shumpei
Published: July 2006

The formation of a component, X, was observed when a reaction mixture of t-butyloxycarbonyl-tryptophan (Boc-Trp), trifluoroacetic acid (TFA), and 1,2-ethanedithiol was analyzed by cellulose TLC. The side product was isolated and further separated into two components by column chromatography on silica gel. The subsequent analysis of the NMR spectra of these components confirmed that they were Nin-But-Trp and Cin-But-Trp. The reaction of Boc-Trp with TFA and with anhydrous hydrogen fluoride (HF) was examined as model systems in order to determine conditions which would minimize the formation of the X component during the synthesis of peptides containing Trp. The addition of 10 molar equivalents of 1,2-ethanedithiol completely suppressed the formation of the X component in HF, but additives were less efficient in TFA. A combination of dimethyl sulfide and 1,2-ethanedithiol was the most effective method for suppressing the formation of the X component in TFA. The behavior of Nin- and Cin-But-Trp in acidic media was also investigated, and a possible pathway for the t-butylation of the tryptophyl residue will be proposed.
13C-NMR Study of the Solvent Effect of the N-Acetyl-l-alanine Methyl Ester
Authors: Asakura Tetsuo , Nishioka Atsuo
Published: July 2006

The 13C-NMR spectra of the N-acetyl-l-alanine methyl ester in solution were observed in order to clarity the solvent effect. The assignment of the two kinds of carbonyl groups was carried out on the basis of the difference in the long-range 1H–13C coupling patterns and the spectral change through the hydrolysis of the ester group in a D2O solution. The internal rotational angle around the N–Cα bond was estimated as −94° from the observed value of 3JC′−N−C″−H, using Bystrov equation. In a trifiuoroacetic acid solution, the formation of strong hydrogen bonds accompanying partial protonation between the N-acetyl-l-alanine methyl ester and the solvent was suggested. Moreover, the acetyl C=O group tends to interact with trifiuoroacetic acid more strongly than the alanyl C=O group.
Phenanthro[4,5-bcd]furan Derivatives. VI. Some Electrophilic Substitution Reactions and Hydrogenation of 4H-Cyclopenta[def]phenanthrene, Phenanthro[4,5-bcd]furan, and 4H-Benzo[def]carbazole
Authors: Horaguchi Takaaki , Yamazaki Reiko , Abe Teishiro
Published: July 2006

Some electrophilic substitution reactions and hydrogenation of 4H-cyclopenta[def]phenanthrene (1a), phenanthro[4,5-bcd]furan (1b), and 4H-benzo[def]carbazole (1c) have been investigated. The bromination of 1a and 1b with bromine gave the corresponding 8-bromo derivatives. The bromination of 1c however gave the 1,3,5,7-tetrabromo derivative as the sole product. The benzoylation of 1a and 1b afforded the corresponding 1-benzoyl derivatives, but in the case of 1c, the 1,7-dibenzoyl derivative was obtained together with the 4-benzoyl derivative. It appears that ortho- and para-orientation of the nitrogen atom in 1c is much stronger than that of the methylene group or the oxygen atom in 1a or 1b. Hydrogenation of 1a, 1b, and 1c with palladium–charcoal catalyst afforded the corresponding 8,9-dihydro derivatives (4a, 4b, and 4c). The reduction of 1a and 1c with sodium–ethanol gave 4a and 4c. The reduction of 1b however gave the 3,3a,8,9,9a,9b-hexahydro derivative. It appears that facile hydrogenation of the carbon-carbon double bonds at the 8,9-positions in 1a, 1b, and 1c are due to strain in the fused ring system.
Layered Compounds. LXII. Triple-layered [m.m][n.n]Paracyclophanes: Syntheses and Spectra
Authors: Otsubo Tetsuo , Kohda Takashi , Misumi Soichi
Published: July 2006

A series of the title cyclophanes (m, n=2–4) were synthesized by the thermal- and photo-desulfurization methods from dithia intermediates. Their absorption and emission spectra were measured to examine the transannular electronic interaction. The absorption spectra of the title compounds and their TCNE complexes gave the same order of the interaction as seen in the case of double-layered system: [2.2]>[3.3]>[4.4] in neutral state and [3.3]>[2.2]>[4.4] in CT state. The emission spectra are discussed in terms of the existence of excited trimer.
Photocyclization of 2′-Hydroxychalcones to 4-Flavanones
Authors: Matsushima Ryoka , Hirao Ichiro
Published: July 2006

On irradiation with light of λ≥365 nm, parent and methoxy-substituted 2′-hydroxychalcones undergo facile photocyclization to give corresponding 4-flavanones in high efficiencies in ethyl acetate or dioxane, whereas in low or nil efficiencies in benzene, chloroform, carbon tetrachloride, ether, acetonitrile, ethanol, or t-butyl alcohol. The low reactivity in benzene is, however, significantly increased by the addition of liquid paraffin to increase the solvent viscosity. 3′,4′-Benzo-2′-hydroxychalcone showed low reactivities in any solvents. The formation of 4-flavanones is neither quenched by triplet quenchers nor depressed by the addition of free radical scavengers. The reaction mechanism is discussed in terms of enolization.
Phenyl- and Tolylthallium(III) Bis(trichloroacetate)s; Preparation and Reactions
Authors: Uemura Sakae , Miyoshi Haruo , Wakasugi Mikio , Okano Masaya , Itoh Osamu , Izumi Takaaki , Ichikawa Katsuhiko
Published: July 2006

Phenyl- and tolylthallium(III) bis(trichloroacetate)s [ArTl(OCOCCl3)2, 1 (Ar=phenyl or tolyl)] were prepared from thallium(III) oxide, trichloroacetic acid, benzene, and toluene. The replacement of the thallium moiety in 1 with iodo, chloro, cyano, selenocyanato, and nitro groups and the aromatic coupling of 1 proceeded smoothly to give the corresponding aromatic derivatives in good yields. In the presence of PdCl2-NaOAc, 1 (Ar=phenyl) reacted with acrylonitrile and methacrylonitrile to afford cinnamonitriles(trans and cis) and a mixture of α-benzylacrylonitrile and β-phenylmethacrylonitriles(Z and E) respectively.
Studies on the Tautomerism of 2-Anilinopyridine and Related Heterocycles. II. 2-Anilino-5-nitropyridine and 2-Anilinopyrimidine
Authors: Hirota Minoru , Sekiya Toshiyuki , Hishikura Akira , Endo Hiroko , Hamada Yoshiki , Ito Yoshio
Published: July 2006

The tautomeric behavior of 5-nitro-2-anilinopyridine and 2-anilinopyrimidine was studied. 2-(N-Methylanilino) and l-methyl-2-(phenylimino)-1,2-dihydro derivatives were prepared as models for the amino and imino tautomers, respectively, and their spectra were compared. The results and the assumed tautomeric equilibrium constants strongly suggest the equilibria to be favorable to the amino tautomers, the Kt values being considerably smaller than that of the parent 2-anilinopyridine.
Photo-cycloaddition of Indene to Chlorofluoroethylenes and Some Reactions Concerning the Adducts
Authors: Kimoto Hiroshi , Takahashi Kensuke , Muramatsu Hiroshige
Published: July 2006

Benzophenone photo-sensitized addition of indene to chlorofluoroethylenes [trichlorofluoroethylene, 1,2-dichloro-1,2-difluoroethylene, 1,1-dichloro-2,2-difluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene] afforded 6,6,7,7-tetrahalogeno-2,3-benzobicyclo[3.2.0]hept-2-enes as corresponding cycloadducts. The structure of the cycloadducts obtained from unsymmetrical chlorofluoroethylenes shows that the addition reaction proceeds with good regioselectivity. Some reactions such as oxidation, reduction, dechlorination, and halogenation of the cycloadducts were also examined.
The Crystal Strycture of the β From of p-Chlorobenzamide
Authors: Hayashi Taiichi , Nakata Kazuaki , Takaki Yoshito , Sakurai Kiichi
Published: July 2006

The crystal of the title compound is monoclinic with space group P21/a, a=9.11, b=9.54, c=8.18 Å, β=93.8°, Z=4. The structure was solved by a packing analysis based on an ellipsoid-model and refined by block-diagonal least-squares calculations to R=0.115. The amide group makes a dihedral angle of 2.0° with the benzene ring.
An ESR Study of Hydrogen Atoms in Methane–Air Flame
Authors: Noda Shoji , Miura Masazumi , Yoshida Hiroshi
Published: July 2006

In order to give a basis for the utilization of ESR in combustion chemical studies, both diffusion flames and premixed flames of a methane–air mixture have been studied by the flame-in-cavity ESR method. A pair of spectral lines separated by 51.0 mT due to H atoms and a very weak single line due to unidentified reaction intermediates have been recorded from combusting gases in a modified Bunsen burner. The H atoms in the diffusion flame give the spectral linewidth of 0.15 mT and populate a confined region near the luminous cone. In the premixed flame, the H atom concentration is the highest at the outside of the luminous inner cone (reaction zone), but it is distributed as long as 4 cm along the gas stream. The profile of the local concentration has been obtained by the deconvolution method from the observed dependence of the spectral intensity on the location of the flame in the resonant cavity. The maximum concentration can be estimated to be 2.4×1015 atoms/cm3, which is much higher than the equilibrium concentration calculated from the flame temperature. 1200 K, and the oxygen excess ratio, 0.67. The spectral linewidth (0.01–0.04 mT) and the microwave power saturation of the H atoms depend on the location in the flame. These results strongly suggest that the line broadening and the spin relaxation are principally determined by the collision between the H atoms and the molecular oxygen.
Thermochemical Studies on Double- and Triple-layered [2.2]Paracyclophanes. Estimation of Molecular Strain Energies.
Authors: Nishiyama Keiichi , Sakiyama Ninoru , Seki Syûzô , Horita Hisanori , Otsubo Tetsuo , Misumi Soichi
Published: July 2006

The measurements of enthalpies of combustion by use of precision oxygen-bomb combustion calorimeter together with the measurement of carbon dioxide recovery were made for double- and triple-layered [2.2]paracyclophanes. The enthalpies of sublimation were also determined by the measurement of temperature dependence of the vapor pressures for the two compounds. The following values are reported for the standard enthalpy of combustion ΔHco(298.15 K)/kJ mol−1 and standard enthalpy of sublimation ΔHso(298.15 K)/kJ mol−1, respectively: double-layered [2.2]paracyclophane, 8729.48±1.80, 99.6±1.8; triple-layered [2.2]paracyclophane, 14230.87±3.59, 125.9±2.5. From analyses of the derived standard enthalpy of formation in gaseous state the following two values for total strain energy Us⁄kJ mol−1 of a molecule of triple-layered [2.2]paracyclophane were obtained: 251.9±5.6 with group method and 245.6±9.8 with chemical similarity method, respectively. These values are approximately twice the magnitudes of the corresponding quantities for double-layered [2.2]paracyclophane. From the analysis of the total strain energy by use of the result of Boyd’s molecular mechanical calculation, the contribution from the twisting of the inner benzene ring to the total strain energy of triple-layered [2.2]paracyclophane was estimated to be almost twice that from one outer bent benzene ring.
ON THE DISSOLUTION VELOCITY OF OXYGEN INTO WATER. PART V. THE OXIDATION VELOCITY OF SODIUM SULPHITE SOLUTION BY OXYGEN IN THE PRESENCE OF THE MOLECULAR FILM OF FATTY ACID
Authors: Miyamoto Susumu , Kaya Tetsuo , Nakata Akira
Published: July 2006

(1) The monomolecular or multimolecular films of stearic acid or of palmitic acid were formed at the upper surface of sodium sulphite solution, and the velocity of the oxidation of sodium sulphite solution was studied, the main body of the solution being well agitated with a stirrer of special construction. It was confirmed that the velocity of the oxidation of sodium sulphite solution by oxygen, observed in the presence of the molecules of these fatty acids, and that observed in the absence of the molecules of the fatty acids, are almost identical under the conditions above described.

(2) A short discussion on the result of the present experiments was made.

The assumption, that a stationary liquid layer is present at the interface between gas and liquid, seems to be unfavourable to the interpretation of the phenomenon observed by the present writers. It was stated that the assumption, that the molecules of fatty acid at the upper surface of the liquid will also be agitated by the stirring of the main body of the liquid and covered with the solution, has great probability for the interpretation of the result of the present experiments.

(3) The mechanism of solution of gas into liquid was shortly discussed.

A part of the opinion of one of the present writers (Miyomoto) on the rate of solution of gases into liquids was described.
STUDIES ON THE FUSED PRODUCTS OF Cr2O3-SiO2 SYSTEM
Authors: Yamaguchi Yohei , Nakazawa Haruo
Published: July 2006

(1) The mixtures of chromic oxide and silica were electrically fused and by the experimental conditions the products of different colours were obtained.

(2) The beautiful green and glassy fused product was obtained only by the second reheating process.

(3) The products of different colours were examined by the petrographic microscope.

(4) The experimental conditions to obtain the each product of different colours were discussed.
ON THE DIBASIC ACIDS IN A FEW SUMACH BERRY WAXES
Authors: Tsujimoto Mitsumaru
Published: July 2006

(1) The crude dibasic acids in urushi wax amounted to about 63% of the fatty acids. Their chief constituent appeared to be eicosane diearboxylic acid, C22H42O4.

(2) Yama-hazé and tsuta-urushi waxes also contained the dibasic acids, which amounted respectively to about 1.6 and 6.3% of the fatty acids. They consisted mainly of heneicosane dicarboxylic acid, C23H44O4.

(3) The fatty acids of yama-urushi wax gave a small amount of a substance of m.p. 102°C. Whether this consisted of the dibasic acids or not, was, however, undecided.
DISPERSOIDOLOGICAL STUDY OF SILVER SALTS IN AQUEOUS ETHYL ALCOHOL, ACETONE AND PROPIONE SOLUTIONS. I
Authors: Ishii Shinjiro
Published: July 2006

In this paper is given a graphical representation of quantitative data pertaining to:

1. The complex solubility of the AgI-precipitate in aqueous ethyl alcohol solutions of KI.

2. The dispergation process in the same solutions.

3. The complex solubility of the AgI-precipitate in aqueous acetone solutions of KI.

4. The dispergation process in the same solutions.
Preparation and Characterization of Cobalt(III) Complexes Containing 1,1,1-Tris(dimethylphosphinomethyl)ethane (mmtp), and the Crystal Structure of [Co(mmtp)2][Co(CN)6]·2.25H2O
Authors: Ando Tadashi , Kita Masakazu , Kashiwabara Kazuo , Fujita Junnosuke , Kurachi Saeko , Ohba Shigeru
Published: July 2006

Eight new cobalt(III) complexes of the type, [CoX3(mmtp)]n+ (mmtp = 1,1,1-tris(dimethylphosphinomethyl)ethane, X3 = (Cl)3, (Br)3, (CN)3, (NH3)3, mmtp, 3-azapentane-1,5-diamine (dien), 1,4,7-triazacyclononane (tacn), and 1,4,7-trithiacyclononane (ttcn)), were prepared and characterized. All of the complexes are stable in the solid state, but the halogeno complexes aquate rapidly in water, and the ammonia complex liberates NH3 slowly in 1 mol dm−3 HCl to give [CoCl2(NH3)(mmtp)]+, other complexes including [Co(mmtp)2]3+ being stable in solution. The crystal structure of [Co(mmtp)2][Co(CN)6]·2.25H2O was determined by X-ray analysis. Crystal data: orthorhombic, space group Pca21, a = 31.579(5), b = 10.521(1), c = 23.458(3) Å, V = 7794(2) Å3, Z= 8, R = 0.084 for 4196 reflections. The Co–P bond distances are 2.291(9)–2.357(7) Å (av 2.331 Å), which are appreciably longer than those usually found in Co(III)–phosphine complexes. The absorption spectra of the complexes were compared with one another and with those of the related complexes.
Synthesis and Intramolecular Electron-Transfer Reaction of Distance-Fixed Quinone-Linked Porphyrins
Authors: Osuka Atsuhiro , Zhang Run Ping , Maruyama Kazuhiro , Yamazaki Iwao , Nishimura Yoshinobu
Published: July 2006

Synthesis is described of a series of distance-fixed quinone-linked porphyrins in which electron affinity of the attached quinone is systematically changed. The fluorescence lifetimes of the porphyrin chromophore in these model compounds were shortened due to the intramolecular electron transfer to the attached quinone. The rates of the charge separation between the singlet excited state of the porphyrin and the quinone were determined on the basis of these shortened fluorescence lifetimes and were plotted against the free energy changes associated with the charge separation. Up to ca. 1.54 eV exothermic reaction, the rates of the charge separation were found to still increase.
Diastereoselective Addition of Grignard Reagents to 3,4-O-Isopropylidene-1-O-triphenylmethyl-l-glycero-2-tetrulose and 1-O-Benzoyl-3,4-O-isopropylidene-l-glycero-2-tetrulose
Authors: Nagano Hajime , Ohno Mina , Miyamae Yoko , Kuno Yukie
Published: July 2006

Diastereoselectivity in the addition of Grignard reagents (RMgX) to 3,4-O-isopropylidene-1-O-triphenylmethyl-l-glycero-2-tetrulose (1) and 1-O-benzoyl-3,4-O-isopropylidene-l-glycero-2-tetrulose (2) depended remarkably on R, X, the solvent, and the reaction temperature. In the reaction of 1 in diethyl ether at 0 °C and 2 in tetrahydrofuran were obtained (2R,3S)-adducts with moderate to high diastereoselectivity, while in the reaction of 2 in diethyl ether at −78 °C (2S,3S)-adducts were the major products. (2R)-2-Hydroxymethyl-2-nonyloxirane and (2S)-2-hydroxymethyl-2-tetradecyloxirane were synthesized.
Selective Friedel–Crafts Alkylation on a Vermiculite, a Highly Active Natural Clay Mineral with Lewis Acid Sites
Authors: Okada Shin-ichi , Tanaka Katsumi , Nakadaira Yasuhiro , Nakagawa Naoya
Published: July 2006

Acid-catalyzed Friedel–Crafts alkylation reactions of p-methylbenzyl chloride with benzene were carried out on four unmodified natural clay minerals. Phenyl-p-tolymethane was quickly and selectively formed in the presence of vermiculite. Although the specific surface area of vermiculite is smaller than those of the other clay minerals examined, such a characteristic property of vermiculite as a catalyst may be attributed to the absence of Brønsted acid sites and to the Lewis acid sites on the outer surface of vermiculite.
Acyliminium Cyclization of Chiral 5-(4-Alkenyl)-5-hydroxy-2-pyrrolidinone Derivatives
Authors: Inouye Yoshinobu , Tazawa Noriko , Watanabe Atsusi , Aoki Yutaka , Kakisawa Hiroshi
Published: July 2006

(3R,4R)-5-(4-Alkenyl)-3,4-bis(benzyloxy)-5-hydroxy-1-methyl-2-pyrrolidinones were cyclized with formic acid to give chiral carbocycles. The 6-membered carbocycle was predominantly formed from (E)-4-alkenyl, while the 5-membered carbocycle was formed from the (Z)-4-alkenyl side chain. One benzyl group was lost during the reaction, resulting in the formation of an ether bridge.
Inclusion Mode of 8-Anilino-1-naphthalenesulfonate (ANS) in the ANS-β-Cyclodextrin Complex
Authors: Nishijo Juziro , Yasuda Masako , Nagai Mayumi , Sugiura Makiko
Published: July 2006

The inclusion mode of 8-anilino-1-naphthalenesulfonate (ANS) in the ANS-β-cyclodextrin complex with a molar ratio of 1 : 1 in deuterium oxide was investigated by measurements of the proton nuclear magnetic resonance spectra and studies with Corey Pauling Koltun models. It was found that in the preferential inclusion mode of ANS, the whole benzene ring of ANS is enclosed at a considerable depth in the cavity of β-cyclodextrin from the side of the secondary hydroxyl group, and a great portion of the naphthalene ring is outside the cavity.
Equation of State for Complex Liquid Mixtures
Authors: Boushehri Ali , Keshavarz Mohammad H
Published: July 2006

The present work shows a successful extension of previous studies to molecular liquids for which the second virial coefficients are not known. Recent advances in statistical-mechanical theory of equilibrium fluids can be used to obtain an equation of state for compressed liquids. The average contact pair distribution function (G), which is at the heart of the equation of state, has the very simple form of a single curve in λb*ρ* (any substance). The effect of many-body forces may still be included in G. The temperature-dependent parameters in the equation can be calculated with reasonable accuracy for most practical purposes just from the experimental heat of vaporization and triple-point density. Thus, thermodynamic consistency is achieved by the use of two scaling parameters (ΔHν, ρt). In terms of these parameters, the reduced second virial coefficient (B2*(T)) obeys a single law of corresponding states in which α*(T) and b*(T) are only slightly modified. The correlations embrace the temperature range Tt ≤ T < Tc and can be used in a predictive mode. The remaining constant parameters are best found empirically from ρt data for pure dense fluids. We tested the equation of state on several liquid mixtures. The results indicate that the density of liquid mixtures can be predicted within about 5% at any pressure and temperature.
Raman Scattering Studies of Vibrational Relaxation in Acetone and 2-Chlorobenzaldehyde
Authors: Bhattacharjee Debajyoti , Ghosh (Purkayastha) Anusree , Misra T N
Published: July 2006

The Raman band of the C=O stretching vibration of acetone and 2-chlorobenzaldehyde has been acquired in a number of solvents of varying physicochemical properties. The effect of solute–solvent dispersion forces on the isotropic frequency shifts has been studied in different solvents (polar and nonpolar both). An attempt has been made to estimate the importance of hydrodynamic and dispersion forces in line broadening of the isotropic component, particularly using the theory of microviscosity.
Conformation of Poly(l-glutamic acid) in Solutions of a Cationic Surfactant with an ω-Hydroxyl Group
Authors: Hayakawa Katumitu , Nagahama Takahiro , Satake Iwao
Published: July 2006

The conformation of poly(l-glutamic acid) was examined based on the circular dichroism spectra in solutions of ω-hydroxyalkylammonium bromides with the dodecyl or undecyl chain and the methyl-, dimethyl- or trimethylammonium moiety, as well as in normal surfactant solutions of dodecylammonium bromides with a corresponding cationic group used as a reference. The conformational change from a random coil to an α-helix was observed, depending on the chain length and head group of the surfactant. A surfactant with a longer chain length induced the α-helix at a lower concentration. A surfactant with more methyl groups has less ability for inducing an ordered conformation, presumably due to a steric hindrance, though it is more hydrophobic. No ordered conformation of poly(l-glutamic acid) was observed in surfactants with the trimethylammonium cationic group.
IR Spectra for Adsorbed CO on Various Alkali Metal Ion-Exchanged ZSM-5 Zeolites
Authors: Katoh Masahiro , Yamazaki Tatsuya , Ozawa Sentaro
Published: July 2006

Carbon monoxide adsorption on alkali metal ion-exchanged ZSM-5 zeolites was investigated by IR spectroscopy. The IR peak positions and intensities of adsorbed CO, and the change in the spectra with temperature are discussed. The IR spectra for physisorbed CO over ZSM-5 zeolites were assigned to the oriented species on a cation, such as M+–C–O and M+–O–C, and the loosely adsorbed CO in the ZSM-5 pore.
Photocatalysis of RhCl(PCy3)2 for Cyclohexane Dehydrogenation: Thermal Dissociation of C–H Bond and Photoelimination of H2
Authors: Itagaki Hiroaki , Murayama Hiroki , Saito Yasukazu
Published: July 2006

Catalytic cyclohexane dehydrogenation, yielding cyclohexene and dihydrogen, proceeded under photoirradiation on either a three-coordinated complex, RhCl(PCy3)2 (Cy = cyclohexyl), or a dihydride complex, RhClH2(PCy3)2, with almost the same turnover frequencies (8.4 or 8.6, respectively) attained by use of a cut-filter (UV-27) under refluxing conditions (354 K). RhCl(PCy3)2 in cyclohexane gave stoichiometric amounts of cyclohexene and RhClH2(PCy3)2 at 354 K; the latter complex yielded little H2 even at 373 K in toluene. A photocatalysis cycle for cyclohexane dehydrogenation with RhCl(PCy3)2 is proposed, where cyclohexene is yielded by thermal C–H bond dissociation and dihydrogen is photoeliminated from RhClH2(PCy3)2, regenerating the original complex.
Intercalation of [Pt(en)2]2+ and [PtCl2(en)2]2+ Ions by Na-Montmorillonite
Authors: Kijima Tsuyoshi , Sakaguchi Kenji , Ohe Kaoru
Published: July 2006

The individual and mixed uptakes of [Pt(en)2]2+ and [PtCl2(en)2]2+ ions by Na-montmorillonite have been studied at 25 °C. In the individual uptakes, the Pt(IV) complex ions are intercalated beyond the cation exchange capacity of the host, which is in striking contrast to the Pt(II) complex ions which are taken up through the capacity. Both complex ions are arranged as a monolayer in which their square-planar PtII(en)2 and PtIV(en)2 planes are parallel and perpendicular to the silicate layers, respectively. The uptake reaction with an equimolar solution of both complexes results in the predominant intercalation of the Pt(II) complex ions, while that with a Pt(IV)-riched mixed solution yields a co-intercalated monolayer in which the Pt(IV) complex ions are held with their square-planar planes tilted by ca. 52° with respect to the silicate layer.
Electrochemical Deposition and Dissolution Processes of Lithium Compound on Gold from Propylene Carbonate
Authors: Yamamoto Nobushige , Hirasawa Hiroshi , Ishida Hidenobu , Tatsuma Tetsu , Oyama Noboru
Published: July 2006

The cathodic electrolysis of propylene carbonate containing lithium perchlorate was studied by means of an in-situ quartz crystal microbalance technique. A lithium compound was deposited at about +1.5 V vs. Li/Li+ and dissolved at about +4.0 V vs. Li/Li+. In constant potential electrolysis at +0.9 V vs. Li/Li+, the deposition process was divided into two stages. In the first stage, in which lithium carbonate was most probably deposited, an electrode reaction of ferrocene which was added to the solution was gradually retarded. In the second stage, in which some chemical reaction proceeded dominantly, the electrode reaction of ferrocene was almost completely blocked. A cathodic charge of +3.0 mC cm−2 was necessary for almost complete blocking.
Oscillatory Chemiluminescence during Peroxidation of Umbelliferone Catalyzed by Horseradish Peroxidase
Authors: Segawa Tadashi , Suehara Shinji , Kamidate Tamio , Watanabe Hiroto
Published: July 2006

The chemiluminescence (CL) which occurred during oxidation of umbelliferone catalyzed by horseradish peroxidase (HRP) oscillated, when a high concentration of H2O2 was employed. The oscillatory CL response reflected periodic changes in the concentration of HRP intermediates between active states, compound I and compound II, and an inactive state of compound III. When the reaction was initiated, the CL was generated by the action of compound I and compound II. Then, the concentration of compound III was gradually increased, because the formation of compound III from compound II and H2O2, the rate constant of which was very little, could not be ignored in a high H2O2 condition; thus the CL was decreased by degrees. Compound III was then decomposed into the active HRP intermediates and the CL was re-increased. The repetition of those processes causes the oscillation. A kinetic study on the mechanism of the oscillatory CL was performed with trial rate equations.