bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies of the Dissolved State of Sodium Tetradecyl Sulfate in Ethanol–Water Mixtures by Measurements of the Activity
Authors: Koshinuma Masakatsu
Published: July 2006

The details of electromotive-force measurement by means of a concentration cell consisting of sodium tetradecyl sulfate (NaTS) in ethanol–water mixtures and of anionic and cationic ion-exchange membranes as septams were described. The membranes used proved to be permeable exclusively to the surfactant (TS−) and Na+ ions respectively. The activities of the TS− and Na+ ions were measured separately, and then the mean activity was computed as a function of the ethanol content in the solvent. Below the CMC, the activities for TS− and Na+ ions and the mean activity increased with an increase in the NaTS concentration, but decreased with an increase in the ethanol concentration. Above the CMC, the activity of the TS− ion decreased, whereas that of the Na+ ion increased; the mean activity also slightly increased with an increase in the NaTS concentration. The values of CMC obtained were 1.5×10−3, 1.7×10−3, and 2.2×10−3 mol/dm3 for 5, 10, and 15 vol % ethanol concentrations respectively. The mechanism of mixed micelle formation was also expressed by a charged phase-separation model in an ethanol–water mixture much as in the case of a simple aqueous solution. The degrees of counterion attachment were found to be 0.73, 0.68, and 0.62 for 5, 10, and 15 vol % ethanol respectively. The intermicellar concentrations of TS−, (CTS), and Na+ ions, (CNa), were calculated. With an increase in the NaTS concentration, CNa monotonously increased, but CNa decreased. At a given NaTS concentration, CNa increased with an increase in the ethanol concentration, while CNa was approximately constant.
The Similarity between the π,π* Absorption Spectra of 1-Indenone and 1,2-Naphthoquinone
Authors: Kuboyama Akira , Matsumoto Hitoshi
Published: July 2006

The π,π* absorption spectrum and its solvent effect of 2-methyl-1-indenone have been found to be similar to those of 1,2-naphthoquinone. This fact is discussed on the basis of the results calculated using the P-P-P method. The similarity of the calculated π-electronic structures in the low-energy π,π* singlet states between 1-indenone and 1,2-naphthoquinone is not so good as that between fluorenone and 9,10-phenanthrenequinone.
Allylic Oxidation of Methyl 2-Alkenoates
Authors: Nakayama Mitsuru , Shinke Shuzo , Matsushita Yoichi , Ohira Susumu , Hayashi Shuichi
Published: July 2006

Allylic oxidation of methyl 2-alkenoates with chromium trioxide in a mixture of acetic anhydride and acetic acid afforded methyl 4-oxo-2-alkenoates.
Conformational Effect on the Bridgehead Reaction of Bicyclo[3.3.1]nonan-2-ones. A Facile Bridgehead Deuteration of a Bicyclo[3.3.1]nonan-2-one Derivative with the Cyclohexanone Ring Locked in the Boat Conformation
Authors: Yamada Kiyoyuki , Manabe Shunichi , Kyotani Yoshinori , Suzuki Masaaki , Hirata Yoshimasa
Published: July 2006

Five bicyclo[3.3.1]nonan-2-ones, two known (1, 3) and three new ones (2, 4, 5) were prepared. The hydrogen-deuterium exchange reaction at the bridgehead position of the bicyclo[3.3.1]nonan-2-one system was examined under mild basic conditions (2 M NaOMe-MeOD, 33 °C, 22 h) using these five bicyclo[3.3.1]nonan-2-ones. Virtually no deuteration took place at the bridgehead in each case of the bicyclic ketones (1, 2, 3, 4), whereas one deuterium was incorporated into the bridgehead of the ketone (5). 13C NMR spectroscopy was employed for the unambiguous determination of the site(s) of deuteration in all cases studied. The enhanced bridgehead acidity of (5) could be explained in terms of the locked boat conformation of the cyclohexanone ring contained in (5).
Nitration of Hexamethylbenzene and Hexamethylbenzene-d18 in Acetic Acid. Deuterium Isotope Effect on the Product Distribution. Mechanism of Side-chain Substitution of Arenes
Authors: Suzuki Hitomi , Mishina Tadashi , Hanafusa Terukiyo
Published: July 2006

The reaction in acetic acid of hexamethylbenzene and hexamethylbenzene-d18 with nitric acid in the dark has been investigated under various conditions using a high-pressure liquid chromatographic method. Pentamethylbenzyl nitrate, pentamethylphenylnitromethane, pentamethylbenzyl acetate, and pentamethylbenzyl alcohol were formed immediately after the mixing of reactants; their relative amounts remained almost unchanged up to nearly 50% conversion. The addition of sodium nitrite gave little influence on the composition of the product mixture, while urea was found to depress somewhat the formation of nitromethane. In the presence of lithium nitrate, the reaction was modestly accelerated and the nitrate formation seems to be slightly favored over the nitromethane formation. Hexamethylbenzene-d18 reacted with nitric acid at the same rate as the non-labeled hydrocarbon did, but the benzyl nitrate/phenylnitromethane ratio in the product mixture was considerably higher in the former. Based on the quantitative data obtained, the mechanism for the side-chain substitution has been discussed in terms of the SN1′ pathway: nitronium ion makes an ipso attack on the substrate to form the arenium ion, which releases a proton from the activated methyl group para to the site of attack to give the 3-methylene-6-nitro-1, 4-cyclohexadiene intermediate (7). Heterolytic fission of the C–N bond in 7 will form a benzyl cation-nitrite anion pair, which recombines at the benzylic carbon atom via a C–N bond or via a C–O bond, giving benzyl nitrite or phenylnitromethane, respectively. Benzyl nitrite will be further converted into benzyl nitrate and benzyl alcohol, while benzyl acetate will arise from the incorporation of solvent molecules into the ion-pair.
Improved Synthesis of Antimycin A3
Authors: Aburaki Shimpei , Kinoshita Mitsuhiro
Published: July 2006

An improved synthesis of antimycin A3 was accomplished by a suitable lactonization of 3-O-benzyl or 3-O-isovaleryl derivative (10a or 10b) of (2R, 3R, 4S)-4-(N-benzyloxycarbonyl-l-threonyloxy)-2-butyl-3-hydroxypentanoic acid, which was synthesized by starting from the corresponding 3-O-benzyl or 3-O-isovaleryl derivative (4a or 4b) of methyl 2-C-butyl-2, 5-dideoxy-β-l-arabinofuranoside, respectively. Acid hydrolysis of 4a or 4b followed by reduction with sodium borohydride afforded 3-O-benzyl or 3-O-isovaleryl-1, 3,4-pentanetriol (5a or 5b), respectively. Tritylation of 5a or 5b followed by succesive 4-O-acylation with N-benzyloxycarbonyl-O-t-butyl-l-threonine, detritylation, oxidation with chromium trioxide-acetic acid-pyridine, and de-t-butylation gave the hydroxy ester acid 10a or 10b, respectively. Lactonization of 10a or 10b through its 2-pyridinethiol ester 11a or 11b activated with silver perchlorate afforded the corresponding nine-membered dilactone derivative 12a or 12b in 33 or 13% yield, respectively. Removal of N,O-protecting groups of 12a by hydrogenolysis, followed by successive N- and O-acylation gave the antimycin A3 precursor, (3S, 4R, 1R, 8R, 9S)-3-(2-benzyloxy-3-nitrobenzoylamino) -4, 9-dimethyl-7-butyl-8-isovaleryloxy-1, 5-dioxonane-2, 6-dione derived from 12b.
Methylation of Pyrimidine 2′-Deoxynucleosides with Trimethyl Phosphate
Authors: Tanabe Toshizumi , Yamauchi Kiyoshi , Kinoshita Masayoshi
Published: July 2006

The reactions of thymidine, deoxyuridine, and deoxycytidine with trimethyl phosphate (TMP) were studied in a homogeneous water solution at 37–60 °C and pH 7–10. Three pyrimidine deoxynucleosides were methylated mainly at the N-3 position to afford their 3-methyl derivatives. The methylation rate at the N-3 position was found to be dependent on the pH of reaction medium. At pH 10, thymidine and deoxyuridine were methylated much faster than deoxycytidine, the tendency being reversed at pH 7.
Kinetic Studies of Spin Trapping Reactions. II. Radiolysis of Cyclohexane
Authors: Doba Takahisa , Noda Shoji , Yoshida Hiroshi
Published: July 2006

In order to extend kinetic utilization of the spin-trapping techniques in radiation chemistry, γ-radiolysis of cyclohexane has been studied at room temperature using pentamethylnitrosobenzene as a spin trap. With increasing radiation dose, the cyclohexyl radical spin adduct has been found by ESR to form and then decay. Consumption of the spin trap has also been monitored by observing the optical absorption. The observed kinetic aspects indicate that the radiation-generated cyclohexyl radicals are completely trapped by 1.3×10−4–6.6×10−4 mol dm−3 of the spin trap, and their G-value is 3.0. The spin-trapping rate constant has been determined to be 1.6×107 mol−1 dm3 s−1 at 299 K based on the reported rate constant for the reaction between the cyclohexyl radical and tributylstannane. From the optical absorption study, dimeric pentamethylnitrosobenzene has been found to dissociate into the monomer, effective in the spin-trapping, with an equilibrium constant of 8×10−4 mol dm−3 in cyclohexane at 299 K. The monomer has an absorption coefficient of 48 mol−1 dm3 cm−1 at its absorption peak of 790 nm.
A Refinement of the Crystal Structure of Creatine Monohydrate
Authors: Kato Yoshihiro , Haimoto Yoshitaka , Sakurai Kiichi
Published: July 2006

The crystal structure of creatine monohydrate has been refined from three-dimensional X-ray data. This refinement introduces minor modifications to the positional and thermal parameters and confirmed the zwitter ion structure.
Effect of Gelatin on the Reduction of Cobalt(II) in Thiocyanate Solutions at Mercury Electrodes
Authors: Itabashi Eiki , Takaya Kumiko
Published: July 2006

Reduction of cobalt(II) in thiocyanate solutions at mercury electrodes has been greatly accelerated in the presence of small amounts of gelatin. This accelerating effect results in an inhibition of the amalgamation of electrodeposited Co(0)SCN−, which reacts chemically to yield CoS and CN−. Both CoS and CN− further stimulate the reduction of cobalt(II).
Absorption and Circular Dichroism Spectra of Bis(ethylenediamine)(1,3-diamine)cobalt(III) Complexes
Authors: Kashiwabara Kazuo , Kojima Masaaki , Arakawa Sumio , Fujita Junnosuke
Published: July 2006

New bis(ethylenediamine)cobalt(III) complexes containing various 1,3-diamines have been prepared and resolved (or separated) into optical isomers. The preferred conformations of six-membered 1,3-diamine chelate rings in these complexes seem to be reflected on the absorption and circular dichroism spectra.
Topological Ligand Design. I. Definition and Derivation of Simple Ligand Graph
Authors: Takamoto Susumu
Published: July 2006

A simple ligand graph and a pattern graph are defined topologically in order to design the patterns of the chelating ligands. This ligand graph, which comprises m donor atoms and n carbon chains capable of forming medium-sized chelate rings, is an irregular graph containing neither multiple lines nor self-loops. All the ligand graphs with m≤8 can be systematically obtained from fifty pattern graphs. These are derived from fifteen basic pattern graphs, which are cubic general graphs containing some multiple lines and self-loops. A pattern code and a set of series indices are tabulated for each ligand graph with m≤8. For the ligand graphs with m≤6, all the geometric isomers of their octahedral chelates are also illustrated.
A Note on the Nature of Ionic Hydrations and Hydrophobic Interactions in Aqueous Solutions
Authors: Arakawa Kiyoshi , Tokiwano Kazuo , Ohtomo Norio , Uedaira Hisashi
Published: July 2006

A theoretical consideration on the nature of solute-water and solute-solute interactions in aqueous solutions has been performed. Thermodynamic functions for the creation of cavities accommodating solute molecules were calculated by the use of the scaled particle theory, and the “negative hydration” effect of univalent ions such as Rb+, Cs+, Cl−, I−  etc., which was proposed first by Samoilov, Krestov and others, was interpreted and discussed. The nature of solute-water and solute-solute interactions in aqueous solutions of inert gases and hydrocarbons was elucidated in comparison with the interactions in nonaqueous solutions of those solutes.
Electrical Properties and Constitution of Several Low-resistivity Iodine Complexes
Authors: Doi Susumu , Fujita Akiyoshi , Ikeura Shigeo , Inabe Tamotsu , Matsunaga Yoshio
Published: July 2006

The electrical resistivity and Seebeck coefficient of the iodine complexes with eight aromatic compounds were examined as functions of the composition and the temperature. The formation of complexes is indicated by maxima or shoulders in the resistivity-composition isotherms at the following compositions: (anthanthrene)2I9, (6,12-dioxoanthanthrene)I2, (6,12-dioxoanthanthrene)I3, (pyranthrene)I3, (violanthrene)2I7, (phthalocyanine)I2, (phthalocyanine)I5, (phenoxazine)2I3, (pyridazine)5I9, and (N,N′-diphenyl-p-phenylenediamine5I13. Furthermore, some sharp resistivity minima are considered as evidence of the complex formation: e.g., (6,12)-dioxoanthanthrene)2I3 and (phthalocyanine)2I3. On the basis of these compositions, a nonintegral formal oxidation state for the organic molecules and the presence of iodine as triiodide or higher polyiodide ions are established for most of the complexes.
Proton NMR Spectra of Selectively Deuterated p,p′-Azoxyanisoles in the Solid State
Authors: Hayamizu Kikuko , Yamamoto Osamu
Published: July 2006

Selectively deuterated PAA’s, PAA-d8, and PAA-d6 have been studied by proton NMR from 77 K to the melting point (390 K). The temperature dependences of T1 the line width, and the second moment for these compounds are presented. It has been demonstrated that PAA is in the rigid state at 77 K on an NMR time scale, and as the temperature increases the two methyl groups begin to rotate about the C3 axis, followed by libration about the C–O axis. There is no evidence for motions of the ring protons except self-diffusion and/or slow reorientation of the molecular axis in the higher temperature range from 286 K to the melting point.
Friedel-Crafts Reaction of Benzene with 2-Phenylpentanedioic Anhydride
Authors: Hashimoto Iwao
Published: July 2006

The reaction of benzene with 2-phenylpentanedioic anhydride in the presence of AlCl3 afforded a mixture of 1,2,3,4-tetrahydro-4-oxo-1-naphthalenecarboxylic acid, 4-benzoyl-2-phenylbutanoic acid and the isomeric 4-benzoyl-4-phenylbutanoic acid. The relative yields among the products were markedly affected by a change in the polarity of the solvent.
Preparation and Spectra of 9-(p-Vinylphenyl)anthracene
Authors: Mukoh Akio , Nozaki Sukekatsu , Hagitani Akira , Morishita Hirosada
Published: July 2006

A novel vinyl monomer containing the polyaromatic ring, 9-(p-vinylphenyl)anthracene, was prepared by the Grignard reaction of anthrone and p-vinylphenylmagnesium halides which could be obtained either from p-bromostyrene or p-chlorostyrene. The results and the spectra of products are discussed.
Preparations and Characterization of Cyclopalladated Complexes of 1-Ethyl-2-phenylimidazole
Authors: Hiraki Katsuma , Fuchita Yoshio , Nakaya Hiroshi , Takakura Shinji
Published: July 2006

Reactions of 1-ethyl-2-phenylimidazole (Hepim) with lithium tetrachloropalladate(II) and palladium(II) acetate give dichlorobis (1-ethyl-2-phenylimidazole, 3-N) palladium (II) and a new cyclopalladated binuclear complex, di-μ-acetato-bis[2-(1′-ethyl-2′-imidazolyl)phenyl, 1-C, 3′-N]dipalladium(II), respectively. The latter complex is readily converted by a metathetical reaction with sodium chloride into a chloro-bridged analogue, [{PdCl(epim)}2]. The chloro-bridged complex reacts with 4-picoline, tertiary phosphines, thallium(I) acetylacetonate, sodium diethyldithiocarbamate, and 2,2′-bipyridyl to give the corresponding mononuclear cyclopalladated complexes. All the complexes prepared in this study are characterized by means of IR, 1H-NMR, and mass spectroscopies.
Preparation and Properties of “β1 and β2”-Isomers of the Salicylato(triethylenetetramine)cobalt(III) Complex
Authors: Yamamoto Yoshihisa , Toyota Eiko
Published: July 2006

β-Salicylato(triethylenetetramine)cobalt(III) chloride monohydrate has been obtained from salicylic acid and β-dichloro(triethylenetetramine)cobalt(III) chloride at pH 10–11. The separation of “β1 and β2” isomers was attempted by using ion exchange. The IR spectra of the “β1 and β2” complexes showed four strong absorption peaks in the 990–1100 cm−1 region. This indicates that the complexes assume the β-form. The 1H-NMR spectrum of ammine protons of coordinated triethylenetetramine of the β1 complex showed six signals with an intensity ratio of 1:1:1:1:1:1, while that of the β2 complex showed five signals with an intensity ratio of 1:1:1:1:2, in 1.8 mol dm−3 D2SO4. The order of the chemical shifts in ppm is N(2)H<N(3)H<N(4)H2<N(1)H2. Thus, the protons of the secondary N(3)H of coordinated triethylenetetramine absorb at lower fields than the terminal N(1)H2 protons. The 13C-NMR spectra of the “β1 and β2” complexes in heavy water showed six signals for trienligand carbons and seven signals for salicylato-ligand carbons. The spectra of these complexes have shown two different configurations of the “β1 and β2” complexes.
α-Chlorination of Long-chain Aliphatic Acids
Authors: Ogata Yoshiro , Sugimoto Toshiyuki , Inaishi Morio
Published: July 2006

Chlorination of long-chain aliphatic acids with a Cl2–O2 mixture in the presence of chlorosulfuric acid at 85 °C gave the corresponding α-chloro acids in good yields (ca. 90%) along with a little amount of aliphatic α-sulfo acids, but no α,α-dichloro acids.
Spectrophotometric Determination of Copper Separated by Means of Adsorption of Its Pyrrolidinedithiocarbamate on Naphthalene
Authors: Fujinaga Taitiro , Takagi Yasuhiro , Satake Masatada
Published: July 2006

The copper chelate of APDC was adsorbed on microcrystalline naphthalene to determine trace amounts of copper. The optimum pH range for the adsorption is 1.5–10.5. The chelate in dimethylformamide has an absorption maximum at 435 nm. Beer’s law holds in the range 2.5–48 μg of copper in 10 ml of dimethylformamide. The molar absorptivity is 1.3×104l·mol−1·cm−1 and the sandell sensitivity 4.8×10−3μg of copper per cm2. Other factors such as amounts of reagent and naphthalene, shaking time, standing time and diverse ions were studied. The method can be applied to the determination of copper in Bovine Liver and human hair.
Ylide-Metal Complexes. III. Preparation and Properties of Gold(I) Complexes of Alkylidenetriphenylphosphoranes and -arsoranes
Authors: Yamamoto Yoshihisa , Kanda Zenjiro
Published: July 2006

Ylide-gold complexes of the type triphenylphosphine(triphenylphosphonium alkylide)gold(I) chloride, (Remark: Graphics omitted.), and bis(triphenylphosphonium alkylide)gold(I) chloride, (Remark: Graphics omitted.), have been obtained from alkylidene triphenylphosphoranes, Ph3P=CH–R (R: H, CH3, CH(CH3)2), and (triphenylphosphine)gold(I) chloride, Ph3PAuCl. Bis(triphenylarsonium methylide)gold(I) chloride, [Ph3AsCH2–Au–CH2AsPh3]Cl, has been synthesized from methylenetriphenylarsorane and Ph3PAuCl. In these organogold complexes, the ylides are attached to the gold atom through the carbanionic donor atom. The 1H-NMR spectra of [Ph3PCH2–Au–PPh3]Cl indicates an intermolecular exchange process in the temperature range +25–−50 °C.
The Extraction of the Chromium(III) Ion from Trichloroacetate Solutions to Inert Solvents Containing Trioctylphosphine Oxide
Authors: Imura Hisanori , Kiba Toshiyasu , Honjo Takaharu
Published: July 2006

Chromium(III) has been extracted with 0.1 mol dm−3 trioctylphosphine oxide(TOPO) in various inert solvents from a 0.1 mol dm−3 trichloroacetate(TCA−) buffer solution of pH 3.5 to 6.0. As diluents of TOPO, hexane and cyclohexane are most effective, while chloroform is quite ineffective. The extraction mechanism has been clarified by analyzing separately the distribution of water, trichloroacetic acid(HTCA), and the Cr(III) ion between the aqueous and organic phases. Water and HTCA are present in the cyclohexane phase as H2O·TOPO and HTCA·TOPO respectively. Chromium(III) is extracted with TOPO into cyclohexane as an ionassociation complex like Cr(H2O)63+(TCA−)3·3TOPO, and the extraction constant is 107.68. It is concluded that the hexahydrated Cr(III) ion is solvated by three molecules of TOPO, forming an ion pair with three trichloroacetate anions. The extractability of Cr(III) in the present system depends most effectively on the concentration of HTCA-free TOPO in the organic phase.
ESR Study of 63Cu(II) Doped in Single Crystals of Bis(alkyl 3-alkylidenedithiocarbazato)nickel(II) and -zinc(II). II. Proton Hyperfine Structure and Tetrahedral Distortion
Authors: Oniki Takayuki
Published: July 2006

The ESR spectra of 63Cu(II) diluted in several single crystals of the title Ni(II) and Zn(II) complexes are reported. In the substituted benzylidene groups, hyperfine structure(hfs) due to the magnetically equivalent two protons have been observed. The hfs were resolvable only in a limited magnetic direction due to the small anisotropic coupling constants. The coordination around Cu(II) ion has been found to be cis in all the Zn(II) complexes and the ESR parameters are more anisotropic than in the Ni(II) complexes. The relationship between the tetrahedral distortion and the ESR parameters has been interpreted using the d-orbital coefficients in the ground state.
Coenzyme Models. 18. Metal Catalysis of NADH Model Reduction in Aqueous Systems
Authors: Shinkai Seiji , Hamada Hisatake , Kusano Yumiko , Manabe Osamu
Published: July 2006

Metal ions (Ni2+ and Zn2+) affected the NADH model reduction of 2-pyridinecarbaldehyde and Schiff bases in aqueous systems. In particular, the rate of the dihydroquinoline reduction of N-(2-pyridylmethylene)-2-pyridylmethylamine was augmented by more than 200-fold, compared with that in the absence of metal ions. On the other hand, the reduction of benzil, ethyl benzoylformate, and trifluoroacetophenone was not subject to the metal catalysis. The enhanced reactivity is accounted for by the affinity of Schiff bases toward metal ions. The efficiency of the metal catalysis was compared with that of the proton catalysis. This is the first example of the systematic examination of the metal catalysis in aqueous systems.
Catalytic Asymmetric Hydroformylation by the Use of Rhodiumcomplexes of Chiral Bidentate Phosphorus Ligands Bearing: Saturated Ring Skeletons
Authors: Hayashi Teruyuki , Tanaka Masato , Ikeda Yoshikazu , Ogata Ikuei
Published: July 2006

(1S,2S)-1,2-Bis(diphenylphosphinoxy)cyclohexane, (1S,2S)-1,2-bis(phosphinomethyl)cyclohexanes, (2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(phosphino) butanes, and (1R,2R)-1,2-bis(phosphinomethyl) cyclobutanes, whose phosphino groups were diphenylphosphino or 5H-dibenzophosphol-5-yl groups where the rotation of phenyl-P bonds is impossible, were used as chiral ligands in rhodium-catalyzed asymmetric hydroformylation. The highest stereoselectivity was attained by the use of (1R,2R)-1,2-bis(5H-dibenzophosphol-5-ylmethyl)cyclobutane or (2R,3R)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(5H-dibenzophosphol-5-yl)butane.
Nucleophilic Ion Pairs. 8. Facile Nucleophilic Cleavage of Dinitrophenyl Sulfate in the Presence of Micellar Zwitterionic Hydroxamates
Authors: Kunitake Toyoki , Sakamoto Tetsuo
Published: July 2006

The sulfate transfer reaction from dinitrophenyl sulfate to hydroxamate nucleophiles was studied in the presence of several types of aqueous micelles at 30 °C, pH 8–9. The zwitterionic hydroxamate was a nucleophile much better than the anionic hydroxamate in the CTAB micelle. The kinetic behavior of the zwitterionic hydroxamate nucleophile was not straightforward and the reactivity of the nucleophile increased with the increase in the relative concentration of the nucleophile and surfactant. These results in the CTAB micelle was analyzed in terms of the two phase model and the rate enhancement relative to the nonmicellar reaction was attributed to substrate binding in the micellar phase and the micellar activation of the hydroxamate nucleophile. The cleavage of dinitrophenyl sulfate by the micellar zwitterionic nucleophile was faster than that by the nonmicellar hydroxamate and the water cleavage by factors of ca. 104 and more than 107, respectively: the fastest cleavage ever observed at the ambient condition.
Reactions of 2-Hydroxyimino-3-methyl-2,3-dihydrobenzothiazole Derivatives with Grignard Reagents and Organolithiums
Authors: Akiba Kin-ya , Shiraishi Hiroaki , Inamoto Naoki
Published: July 2006

Reactions of 2-hydroxyimino-3-methyl-2,3-dihydrobenzothiazole derivatives (1) with Grignard reagents gave 2-hydroxyimino (1e) and 2-(substituted imino)-3-methyl-2,3-dihydrobenzothiazoles as major products, where 1e was reduced by excess Grignard reagents to 2-imino derivative. On the other hand, reactions of 1 with organolithiums afforded o-(methylamino)phenyl sulfides as a major product.
Functionalization of trans-Decalin. III. A Stereospecific Preparation of Vicinal cis Two Methyl Groups of Eremophilane Skeleton, Leading to dl-Dehydrofukinone
Authors: Torii Sigeru , Inokuchi Tsutomu , Yamafuji Tetsuo
Published: July 2006

A procedure for the preparation of dl-dehydrofukinone (1), an eremophilane type sesquiterpene, from the diene adducts (3), prepared from the reaction of 4-methyl-3-methoxycarbonyl-2-cyclohexen-1-one with butadiene, is described. Acetalization-reduction (LiAlH4) of 3 followed by treatment of the corresponding mesylate with base provided 5,6-cis-5-methyltricyclo[4.4.1.01,6]undec-8-en-2-one (7) in 69% overall yields. Reductive cleavage of 7 with lithium metal afforded trans-4β,4aβ-dimethyl-Δ6,7-octalin-1-one (8), bearing a set of vicinal cis two methyl groups on the C-4 and C-4a carbons in an 83% yield. Functionalization of the double bond of 8 involves (1) reduction of carbonyl group and following tetrahydropyranylation, (2) epoxidation followed by regiospecific reduction of the oxirane ring at the C-6 position, and (3) subsequent oxidation of the hydroxyl group, giving trans-4aβ,5β-dimethyl-8β-tetrahydropyranyloxydecalin-2-one (14b) in good yields. The conversion of 14b into the desired 1 was achieved smoothly by (1) hydrolysis of tetrahydropyranyl ether, (2) pyrolysis of its mesylate, and (3) subsequent aldol reaction with acetone followed with dehydration and isomerization of the double bond.
Synthesis of α-Trialkylsilyl Ketones
Authors: Obayashi Michio , Utimoto Kiitiro , Nozaki Hitosi
Published: July 2006

The isomerization of 2-trimethylsilyl-2,3-dialkyloxiranes occurs in the presence of MgI2 to give α-trimethylsilyl ketones only, if one starts from (2S*,3S*)-isomers. In contrast, however, the reaction of (2S*,3R*)-oxiranes produces enol silyl ethers in addition to α-trimethylsilyl ketones. The reaction proceeds via the Mg salts of regioand stereoselectively produced β-iodo-β-trimethylsilyl alcohols, each diastereomer of which behaves differently. Remarkably, Li salts of both iodohydrins [(2S*,3S*)- and (2S*,3R*)-isomers] give α-trimethylsilyl ketones exclusively. This provides efficient procedures for preparing α-trimethylsilyl ketones from a mixture of diastereomeric silyloxiranes.
Syntheses of Steroidal π-Allyl Palladium Chloride Complexes
Authors: Satoh J Yasuo , Horiuchi C Akira
Published: July 2006

The reaction of the following steroidal olefins with palladium(II) chloride in the presence of potassium acetate in acetic acid afforded the corresponding steroidal π-allyl palladium chloride complexes: 5α-cholest-1-, -2-, and -3-ene; cholest-4- and -5-ene; 3-methyl- and 3-phenyl-5α-cholest-2-ene; 3β-chloro- and 3β-acetoxycholest-5-ene; and 5β-cholest-1-, -2-, and -3-ene.
Enantioface-differentiating (Asymmetric) Hydrogenation of Keto Ester with Modified Nickel Catalyst. XXXII. Structural Requirements of Modifying Reagent and Substrate
Authors: Okamoto Shinji , Harada Tadao , Tai Akira
Published: July 2006

The enantioface-differentiating hydrogenation of α-, β-, γ-, and δ-keto esters over α-, β-, and γ-amino acid–MRNi has been conducted. The optimum enantio-differentiating power of α-amino acid-MRNi has been found in the hydrogenation of the β-keto ester and that of β-amino acid-MRNi found in the hydrogenation of the γ-keto ester. The results have been explained in terms of the intermolecular recognition between substrate and modifying reagent through the functional groups.
The Liquid-phase Oxidation of Hydrocarbons with Molecular Oxygen. II. A Highly Selective Formation of α-Tetralone by the Metal-catalyzed Oxidation of Tetralin in the Presence of N,N-Dialkylamides
Authors: Mizukami Fujio , Horiguchi Yutaka , Tajima Masaki , Imamura Juichi
Published: July 2006

The metal-ion catalyzed oxidation of tetralin was carried out in different solvents in which metal salts tend to be soluble. It was found that, for the production of α-tetralone, a chromium salt is the best catalyst among the first-transition-metal salts employed, while N,N-dialkylamides are the best solvents or the best additives. For example, in the tris(acetylacetonato)chromium(III)-catalyzed oxidation of tetralin in the presence of N,N-dimethylacetamide, α-tetralone was obtained in a 93.0% yield at a 27.2% tetralin conversion. The decomposition of α-tetralyl hydroperoxide (THP) with different first-transition-metal catalysts was also carried out in N,N-dimethylformamide in order to elucidate the formation mechanism for α-tetralone in the oxidation of tetralin in the presence of N,N-dialkylamides. It was concluded that the product distribution in the oxidation mainly depends on the decomposition mechanism of THP, and that N,N-dialkylamides seem to promote the reaction of the α-tetralylperoxyl radical with low valent metal ions, ROO·+Mn+→α-tetralone+OH−+M(n+1)+.
Studies on Inorganic Precipitate Membranes: Membrane Potential and Bi-ionic Potential
Authors: Beg M Nasim , Siddiqi Fasih A , Singh Surendra P , Gupta Veena , Prakash Poorna
Published: July 2006

Electrical potentials arising across barium(II) phosphate, mercury(II) iodide and cobalt(II) chromate membranes using various 1:1 electrolytes are reported. Thermodynamically effective fixed charge density, which is an important parameter governing the membrane phenomena, has been evaluated by the theory of Toyoshima and Nozaki. Using the values of effective fixed charge density determined, the theory of bi-ionic potentials developed by Toyoshima and Nozaki based on the principles of the irreversible thermodynamics has been examined. Theoretical predictions were borne out quite satisfactorily by our experimental results.
Kinetics and Mechanism of Formation of Pentaammine(glycine)rhodium(III) Ion from Pentaammineaquarhodium(III) Ion and Glycine in Weakly Acidic Media
Authors: Chatterjee C , Basak A K
Published: July 2006

The rates of formation of pentaammine(glycine)rhodium(III) ion from pentaammineaquarhodium(III) ion and glycine in weakly acidic media have been studied spectrophotometrically at different glycine and acid concentrations in the temperature range of 60–80 °C. The rate has been found to be insensitive towards the change in ionic strength from μ=0.5 to 2.0 M of the medium. The activation parameters, ΔH\eweq and ΔS\eweq values are 22.2±1.0 kcal mol−1 and −9.2 e.u. respectively. The results are in accord with a mechanism involving a fast 1:1 outer-sphere association between the pentaammineaquarhodium(III) ion and glycine in zwitter ionic form followed by its transformation into the product by a process where the incoming ligand is appreciably bonded to the metal ion in the transition state.
Studies on Uranyl Complexes. II. Unidentate Carboxylate Coordination in Uranyl Complexes of α-, β-, and γ-Amino Acids: A Polarographic Study
Authors: Ramanujam V V , Rengaraj K , Sivasankar B
Published: July 2006

Polarographic investigation of uranyl complexes with potentially bidentate α-, β-, and γ-amino acids have been carried out. The polarographic behaviour of these complexes as a function of pH and ligand concentration has revealed the nature of binding to be unidentate carboxylate coordination in the complexes. The amino group is not involved in coordination. The relative stabilities of α-, β-, and γ-amino acid complexes are discussed.
Isomerism of the Metal Complexes Containing Multidentate Ligands. VIII. Chromatographic Behavior of [CoN6]3+-type Complexes on an SP-Sephadex Column
Authors: Sakakibara Katsumi , Yoshikawa Yuzo , Yamatera Hideo
Published: July 2006

An empirical rule is presented for the elution order of [CoN6]3+-type complexes in chromatography on SP-Sephadex columns. The relative elution rates have been correlated with the number and the kind of the octahedral faces of the complex on which ion association with a phosphate ion occurs.
Preparation of Anhydrous N,N′-Dicyclohexylalloxan and Its Use in Dehydration
Authors: Endo Takeshi , Okawara Makoto
Published: July 2006

Anhydrous N,N′-dicyclohexylalloxan has been prepared and used as a dehydrating agent for carboxylic acids in the esterification of carboxylic acids with alcohols.
Configuration et Conformation en Solution de Quelques α-Hydroxyiminocetones Cycliques
Authors: Bernadou Jean , Bonnafous Monique
Published: July 2006

Les dérivés α-hydroxyiminés des cyclanones en C6 (un isomére), C8 (deux isoméres) et C12 (un isomére) ont tous la configuration anti ; la conformation est variable selon la taille du cycle: s-cis pour le terme en C6, s-cis ou s-trans pour les termes en C8, s-trans pour le terme en C12.
The Relationship of π-Binding Energy with Molecular Connectivity in Hydrocarbons
Authors: Gupta Satya P , Singh Prithvi
Published: July 2006

Hückel’s π-binding energy, Eπ, in hydrocarbons is found to be parallel to Kier’s molecular connectivity index, χ. In either class of hydrocarbons, alternant or non-alternant, the regression analysis reveals a highly significant linear correlation between Eπ and 1χv (the first order valence connectivity index).
The Reaction of Copper(I) Methyltrialkylborates with 1-(1-Pyrrolidinyl)-6-chloro-1-cyclohexene
Authors: Yamada Kinji , Yano Takashi , Miyaura Norio , Suzuki Akira
Published: July 2006

The reaction between copper (I) methyltrialkylborates readily obtainable from organoboranes and 1-(-1-pyrrolidinyl)-6-chloro-1-cyclohexene was found to give corresponding alkylation products which are readily hydrolyzed to alkylated cyclohexanones.
Oxidation of 3,5-Di-t-butylcatechol Catalyzed by Metal Acetylacetonates in Organic Solvents
Authors: Sakamoto Hiroyuki , Funabiki Takuzo , Yoshida Satohiro , Tarama Kimio
Published: July 2006

The oxidation of 3,5-di-t-butylcatechol (3,5-DTBC) has been studied in organic solvents in the presence of metal acetylacetonates (M(acac)2). The catalytic activity of M(acac)2 decreased in the order M=Mn>Co>Ni>>Fe, and the product was 3,5-di-t-butyl-o-benzoquinone (3,5-DTBQ). The kinetic analysis has suggested a mechanism in which the radical chain reactions involving 3,5-di-t-butyl-o-benzosemiquinone (3,5-DTBSQ·) and hydroperoxyl radical (·OOH) are initiated by the reaction of 3,5-DTBC with the initially formed dioxygen metal complexes. Kinetic parameters for the complexation of molecular oxygen by Mn(acac)2 and Co(acac)2 were estimated: ΔH\eweq(kJ mol−1)=4.6±0.8 for Mn, 29.7±0.8 for Co; ΔS\eweq(J mol−1K−1)=−200±2 for Mn, −135±2 for Co.
The Oxidation Activity and Acid-Base Properties of CO3O4–V2O5 and CO3O4–MoO3 Systems
Authors: Ai Mamoru
Published: July 2006

The acidity and basicity of Co3O4–V2O5 and Co3O4–MoO3 systems, with different compositions, were measured by means of the adsorption of NH3, pyridine, and CO2. The values of acidity were also confirmed by studying the catalytic activity for acid-catalyzed reactions, such as the dehydration of isopropyl alcohol and the isomerization of 1-butene. With the addition of V2O5 or MoO3, the basicity rapidly decreases and the acidity gradually increases. The catalytic activity for the oxidation of hexane is well correlated with the basicity of the catalysts. With the Co3O4-rich catalysts, V/(Co+V) or Mo/(Co+Mo)<0.4, butadiene is mainly oxidized to CO2; the rate is also correlated to the basicity. However, the Co3O4-poor catalysts, V/(Co+V) and Mo/(Co+Mo)>0.6, show a good selectivity for the maleic anhydride formation. The Co3O4-containing catalysts, regardless of the composition, are not effective for the selective oxidation of butene to butadiene. In the oxidation of methanol, the Co3O4-rich catalysts give only CO2. However, with the Co3O4-poor catalysts, formaldehyde is almost the sole product. It is concluded that the catalytic behavior is to be interpreted, to a considerable extent, in terms of the acid-base properties of the metal oxides.
Correlation between Electron Capture Response and Chemical Structure for Benzyl Chlorides
Authors: Kojima Tsugio , Satouchi Masaru , Tanaka Yasukazu
Published: July 2006

In the dissociative electron capture reaction of benzyl chlorides, all the substituents in the para position except for t-butyl group tend to decrease the activation energy, those in the meta position having no influence on the activation energy. This can be explained in terms of the contribution of a para substituent to the stabilization of the incipient radical in the transition state resulting from the delocalization of the odd electron. The resonance effect of the para substituent was compared with that obtained in the phenylation of substituted benzenes with phenyl radical, where phenylcyclohexadienyl radical is formed as an intermediate. The resonance effects in these two reactions agree, supporting the reaction mechanism proposed.
The Kinetics of Oxygen Exchange between Arsenate Ions and Water. III. Catalysis by Periodate Ions
Authors: Okumura Akiko , Watanabe Seiko , Sakaue Miyoko , Okazaki Nobukazu
Published: July 2006

Oxygen exchange between arsenate ions and water is remarkably catalyzed by the addition of a small amount of periodate ions. The reaction has been studied at 30.0 °C over the pH range of 6.7–11.4. The rate law of the catalytic reaction has been found to be Rc=k·[H+][As(V)][I(VII)], where Rc is defined as the increase in the rate of oxygen exchange of arsenate ions by the addition of periodate ions. The catalytic process has been interpreted in terms of the reversible condensation of arsenate ions with periodate ions to form the arsenatoperiodate ions, and the rate constant of the condensation reaction between H2AsO4− and H4IO6− has been estimated to be 340 M−1 s−1 at 30.0 °C.
Electronic Absorption Spectra and Geometry of Radical Ions of Tetraphenylethylene
Authors: Suzuki Hiroshi , Koyano Kinko , Shida Tadamasa , Kira Akira
Published: July 2006

The geometry of the radical ions of tetraphenylethylene was studied by means of electronic absorption spectroscopy. The spectrum of the anion radical produced by γ-ray irradiation in frozen 2-methyltetrahydrofuran changes markedly on controlled warming. The resultant spectrum resembles the spectra of the anion radical in fluid solutions produced by potassium reduction and by pulse radiolysis. These spectra are distinctly different from the spectra of diphenylmethanide ion and of diphenylmethyl radical. From these facts it is inferred that the relaxed anion radical has a geometry in which the central ethylenic bond is twisted by an angle considerably smaller than 90°, in contrast with the near 90° twist in the dianion, and in which each bond connecting a phenyl group with an ethylenic carbon atom is twisted by a smaller angle than in the molecule. The spectrum of the cation radical produced by γ-ray irradiation in frozen matrices is similar to that of the cation radical produced by pulse radiolysis in fluid solutions and changes only slightly on controlled warming. The geometry of the relaxed cation radical is suggested to be similar to that of the molecule, in contrast with that of the anion radical.
The Mass-transfer Rate through the Liquid–Liquid Interface. VII. Diffusion through a Spherical Interface Involving the Adsorption-Desorption Process
Authors: Shimbashi Teruya
Published: July 2006

A theoretical formula for the transfer rate of a solute through a spherical interface has been proposed, considering the adsorption-desorption process and the variation in the amount of adsorption. Computational results indicate that, in the usual particle-diameter (radius<1 mm), the diffusion coefficient has practically no relation to the transfer rate in the case of a significant interfacial resistance, such as is observed in the transfer of fatty acids. The concentrations of butylamine in the aqueous, continuous phase in a stirred extraction vessel have been predicted.
Direct Measurement of Interaction Energy between Solids and Gases. IV. Acidic and Catalytic Properties of Amorphous and Crystalline Alumino-silicates
Authors: Masuda Tatsuo , Taniguchi Hitofumi , Tsutsumi Kazuo , Takahashi Hiroshi
Published: July 2006

Surface acidities and acid strength distributions of amorphous silica–alumina, Y-type faujasite and mordenite have been examined by measuring the differential heats of adsorption of ammonia. The number of acid sites with adsorption heats higher than 70 kJ/mol increased in the order: NH4Y>NH4M>RENH4Y>silica–alumina. On the other hand, the order of the acid strength was: NH4M>RENH4Y>silica–alumina>NH4Y. The high catalytic activities of zeolites for cumene cracking and toluene disproportionation were correlated with acid strength, Bronsted acidity, and electrostatic effect.
Decay of Naphthalene Phosphorescence in the Presence of Some Chlorinated Compounds. An External Heavy Atom Effect
Authors: Ebara Nozomu , Yajima Yusuke , Watanabe Hiroshi
Published: July 2006

The decay of the phosphorescence of naphthalene in the mixed solutions of methylcyclohexane and several chlorinated compounds has been analyzed. In many cases the decay was almost exponential and the decay constant was a function of the concentration of chlorinated compounds. In the case of carbon tetrachloride, the decay was distinctly non-exponential. The decay was analyzed by a Laplace transformation method. In this case a complex was formed, in equilibrium with the free naphthalene molecule, and the decay constant of the former increased when the concentration of CCl4 increased. The external heavy atom effect takes place in two ways: one by complex formation with the molecule containing heavy atoms and another by a long range interaction through a statistical distribution of the latter molecules around the phosphorescing molecule.
A Molecular Orbital Approach to the Electrophilicity of H and OH Radicals
Authors: Imamura Akira , Hirao Kimihiko
Published: July 2006

We tried to explain the electrophilicity of radical reagents such as H and OH radicals in the aromatic substitution reaction by using the molecular orbital theory. The delocalization energy of π electrons was decomposed into two parts: one is the energy due to the delocalization from a substrate to a reagent and another is that from a reagent to a substrate. The former was considered to be a measure of the electrophilicity and the latter of the nucleophilicity. The decomposition of the delocalization energy into two parts was carried out by modifying the relevant core resonance integrals as appropriate. The result indicated that the delocalization energy for the electrophilicity was much larger than that for the nucleophilicity for both radicals. Thus, H and OH radicals should be electrophilic in nature, in good agreement with the experimental facts. Finally, the origin of the electrophilicity was discussed in connection with the height of the relevant energy levels by following a perturbational approach.
Raman Spectra of a Compound under Inversion Motions: N,N′-Dimethylpiperazine
Authors: Fukushima Kunio
Published: July 2006

Raman spectra of methanol and aqueous solutions of N,N′-dimethylpiperazine were measured. Forms of stable conformers in various states were studied by comparison of the spectra obtained under various conditions. It was found that hydrogen bonding to nitrogen atoms of N,N′-dimethylpiperazine causes a conformational change.
An Application of Neutron Activation Analysis to Biological Materials. III. Natural Abundance of Small and Micro Amounts of Elements and Their Interactions in Human Tissues
Authors: Terai Minoru , Akabane Akiko , Matsumoto Michio , Hashimoto Keisuke
Published: July 2006

The natural abundance of the principal inorganic elements in five human tissues (brain, kidney, lung, liver, and heart) have been determined by neutron activation analysis. Cl, K, and Mn are equally distributed in all tissues. The highest concentration of Sc(0.22±0.044 ppm) is found in the liver. V(0.64±0.51 ppm) and Cr(0.19±0.11 ppm) concentrations in the lung are significantly higher than in other tissues at a 95% confidence level. The lowest concentration of Br(2.7±1.8 ppm) is found in the brain. The highest concentration of Cd(74±11 ppm) appears in the kidney and differs significantly from that in other tissues. Significant correlations appear to exist between many pairs of elements in the kidney and the lung, whereas there are relatively few in the liver. The normal significant correlations between Na, Cl, K, Sc, Zn, Se, Cd, and other elements are given.
Liquid Structure of Carbon Tetrachloride and Long-range Correlation
Authors: Nishikawa Keiko , Murata Yoshitada
Published: July 2006

The diffraction of liquid CCl4 was measured by using the energy-dispersive X-ray diffractometer. The fine structure was observed for the first time in the present study. The existence of the fine structure in the diffraction pattern shows the long-range correlation “directly.” The bcc cluster model for liquid CCl4 is presented on the basis of the long-range correlation. The calculated intensity of the model is in good agreement with the observed one.
Studies on Biologically Active Pteridines. II. Synthesis of Some 2-Pyrimidinyl- and 2-Pteridinyl-amino Acids
Authors: Sugimoto Takashi , Shibata Keiko , Matsuura Sadao , Nagatsu Toshiharu
Published: July 2006

Synthesis of some pyrimidines and pteridines with an amino acid residue at the 2-position was investigated. 4-Ammo-6-hydroxy-2-methylthio-5-nitrosopyrimidine, on heating with amino acids in water, underwent aminolysis at the 2-position to give the corresponding N-(4-amino-6-hydroxy-5-nitroso-2-pyrimidinyl) amino acids. These (5-nitroso-2-pyrimidinyl)amino acids, after reduction of the nitroso group to an amino group, condensed with biacetyl or a pentose phenylhydrazone to give N-(4-hydroxy-6,7-dimethyl-2-pteridinyl) amino acids and N-(4-hydroxy-6-polyhydroxypropyl-2-pteridinyl) amino acids, respectively.
An Examination of the Displacement Reactions in Alkyldicyclohexylborane and Alkyldi-exo-norbornylborane
Authors: Taniguchi Hiroaki
Published: July 2006

Displacements involving the reaction of olefins with alkyldicyclohexylborane and alkyldi-exo-norbornylborane were studied. In the case of alkyldicyclohexylborane, the 1-ethylbutyl group could be displaced selectively by 1-decene to produce hexenes. However, the hexyl group could not be displaced selectively, the reaction proceeding to produce both 1-hexene and cyclohexene. In contrast, in the case of alkyldi-exo-norbornylborane, the norbornyl group bonded so tightly to the boron atom that it was possible to displace both the 1-ethylbutyl and the hexyl groups selectively and completely by 1-decene with no loss of 2-norbornyl-boron bonds. The results suggest the possibility of contrathermodynamic isomerization of olefins by the combination of “isomerization-displacement” with di-exo-norbornylborane.
New Applications of Crown Ethers. I. Primary Alkylamine–Water–Crown Ether System as a Hydroxide Ion Source in the Reduction with Carbonylhydridoferrate Anion
Authors: Wada Fumio , Ishihara Ryoji , Kamohara Yasufumi , Matsuda Tsutomu
Published: July 2006

Utility of the primary alkylamine–water–crown ether system as an effective source of hydroxide ion was studied by the reduction of benzylideneacetone with carbonylhydridoferrate anion. Excellent conversion and selectivity for the reduction were attained in a two-phase system (benzene–water) in the presence of dicyclohexano-18-crown-6, comparable to those obtained with use of potassium hydroxide in place of the amine. Effects of several alkylamines and crown ethers were presented. IR examination of pentacarbonyliron–butylamine-water in benzene with or without the crown ether showed that the presence of the crown ether markedly alters the route of formation of the reducing agent (s).