bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Codimerization of Butadiene and Ethylene Catalyzed by Cobaltous Chloride-Ditertiary Phosphine Complexes-Grignard Reagent-ROH. Effects of Ditertiary Phosphine Ligands and Alcohols
Authors: Kagawa Teruhiko , Hashimoto Harukichi 
Published: July 2006

Abstract
Butadiene-ethylene codimerization is accomplished by means of the catalyst derived from the reactions of CoCl2(Ph2P(CH2)nPPh2)m with a Grignard reagent and then with appropriate amounts of alcohols to obtain 1,4-cis-hexadiene selectively. The yield of 1,4-hexadiene depends on the number of ditertiary phosphine ligands (m), the methylene-chain length of the ligand (n), and the kind of alcohol. A hydride complex, HCo(Ph2P(CH2)2-PPh2)2 also has codimerization activity in the presence of both n-PrMgCl and alcohols. It is considered that the resulting alkoxymagnesium chloride activates the catalyst.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. VI. Syntheses and Electronic Spectra of 6,6′-Dichrysenylpoly-ynes
Authors: Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
6,6′-Dichrysenylpoly-ynes (In, n=1–6) have been synthesized and their electronic spectra were measured. It was found that the bathochromic shifts of the longest-wavelength absorption peaks (λmax) along with an increase in the number of acetylenic bond (n) were proportional to n1.6 (λmax=5.8n1.6+394nm).
Base-catalyzed Condensation of o-Nitroacetophenone. V. Hydrogenation of Compound A, a Condensation Product. Formation of a 4-Quinolone from an Indoline System
Authors: Miwa Toshio 
Published: July 2006

Abstract
The catalytic hydrogenation of compound A, a base-catalyzed condensation product of o-nitroacetophenone, followed by treatment of the product with acid gave a 4-quinolone. The quinolone proved to be 2-[1-(o-aminophenyl)-1-hydroxyethyl]-4-quinolone by the oxidative degradation of the corresponding quinoline derivative.
Aminocyclitols. XXVIII. Bromination of Inosamines and Inosadiamines
Authors: Suami Tetsuo , Ogawa Seiichiro , Yanagida Shinichi , Nojima Kazuhiro 
Published: July 2006

Abstract
Bromination of four inosamines (myo-2 (1), chiro-1 (2), muco-1 (3), and scyllo (4)) and three inosadiamines (neo-1,4 (11), muco-1,5 (14a,b), and muco-1,4 (19)) with acetyl bromide and acetic anhydride in a sealed tube at 130–160°C has been studied. 2,5-Dibromo-2,5-dideoxy-chiro-inosamine-3 tetraacetate (8), was obtained from 1,2, and 3, and, as a monobromide, only 2-bromo-2-deoxy-chiro-inosamine-3 pentaacetate (7) could be isolated from the bromination product of 3. From 11, monobromide (12) and dibromide (13) were obtained. From 14a or 14b, 2-bromo-2-deoxy-chiro-inosadiamine-3,5 pentaacetate (15) was obtained, and, under a more drastic condition, 15 was further brominated to afford 1,5-dibromo-1,5-dideoxy-chiro-inosadiamine-2,4 tetraacetate (16). The bromo compounds so obtained were converted into the corresponding deoxy or dideoxy derivatives by hydrogenolysis. All the structures of the new compounds have been confirmed on the basis of proton magnetic resonance (PMR) spectroscopy using their acetyl derivatives. Considering from the structures of the bromides, a mechanism of a bromination reaction has been proposed.
Total Syntheses of Carbohydrates. III. Dl-Glyceraldehyde and 2-Deoxy-Dl-erythro-pentose
Authors: Mimaki Kosuke , Masunari Michihiko , Nakaminami Gen , Nakagawa Masazumi 
Published: July 2006

Abstract
The synthesis of Dl-glyceraldehyde (III) by the Barton’s oxidation of Dl-isopropylideneglycerol (I) was described. 2-Deoxy-Dl-erythro-pentose (IX) (2-deoxy-Dl-ribose) has been synthesized by the Barton’s oxidation of 2-deoxy-3,4-O-isopropylidene-5-O-(tetrahydro-2-pyranyl)-Dl-erythro-pentitol (VIII) and by the hydroboration of Dl-erythro-4-pentyn-1,2,3-triol (XI) followed by hydrogen peroxide oxidation. The latter method gave crystalline 2-deoxy-Dl-erythro-pentose (IX) in a reasonable yield.
The Epoxidation of Homoallylic Alcohols and the Formation of Sesquiterpene Diols
Authors: Yamamura Shosuke , Iguchi Masanobu , Niwa Masatake , Hirata Yoshimasa 
Published: July 2006

Abstract
The epoxidation of homoallylic alcohols was effected with m-chloroperbenzoic acid in ether, and the resulting epoxides were reduced with lithium aluminum hydride to the corresponding diols. Particularly in the cases of calameone and isocalamendiol, the exocyclic double bond at the C3-position was attacked by the peroxy-acid from the side opposite to the axial hydroxyl group at the C5-position.
Kinetic Studies of Intermolecular Hydrogen Bonding in Carboxylic Acids by Means of Ultrasonic Absorption Measurement. I. Fatty Acids
Authors: Sano Takayuki , Tatsumoto Nobuhide , Niwa Toshio , Yasunaga Tatsuya 
Published: July 2006

Abstract
The ultrasonic absorptions in n-butyric, isobutyric, n-valeric, isovaleric, and n-caproic acids have been measured in the frequency range from 2.5 to 95 MHz in order to study the relationship between the ultrasonic absorption and the chemical structure of the alkyl group in carboxylic acids. The relaxation absorptions were observed for all the acids with relaxation frequencies in the range of 1.6–8.7 MHz. The kinetic parameters have been calculated on the basis of an assumption that the absorptions are associated with the breakage of one of the two hydrogen bonds in the dimer, as in the case of propionic acid. The values of the heat of reaction, ΔH, were calculated to be 4.7–6.4 kcal per mole of dimer. By an application of the results to Taft’s equation, logK=ρ*σ*+sEs, it is deduced that the change in the ΔH in a series of monocarboxylic acids is due to variations in the inductive effect of each alkyl group. However, the change in the heat of activation, ΔH≠, can not be explained in terms of the inductive effect.
A New Theory of Melting at High Pressures
Authors: Kanno Hitoshi 
Published: July 2006

Abstract
As an improvement of the significant structure theory, a new partition function of monatomic liquid was derived:
Zl(T, Vl)=\left{\overset3Nv\underseti=1Π\left[2sinh\left(\frachνi2kT\ight)\ight]−1\ight}\left{\left(\frac2πmkTh2\ight)3⁄2\fraceVfNt\ight}Ntexp\left{\fracΦl(Vl)kT\ight}
where 3Nv and 3Nt, (Nv+Nt=N; Avogadro number), are the numbers of freedom in vibrational and translational motions, respectively, vi the i-th normal vibration in the vibrational motion, m the mass of molecule, Vf the free volume of liquid, and Φl(Vl) the configurational potential energy of liquid. Melting of argon at high pressures is successfully interpreted by means of the partition function.
Studies on the Interaction between Long Chain Alcohols and Alkyl Sulf ates. II. Molecular Association between Dodecyl Alcohol and Dodecyl Sulfate of Divalent Metals
Authors: Moroi Yoshikiyo , Motomura Kinshi , Matuura Ryohei 
Published: July 2006

Abstract
Molecular interaction between dodecyl alcohol and dodecyl sulfate of divalent metal cations such as Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, and Cu2+ was studied by measurement of heat of complex formation, differential thermal analysis and infrared spectroscopy. It was found that magnesium, manganese, cobalt, nickel, and copper dodecyl sulfates formed two or three kinds of complexes with dodecyl alcohol, differing in composition depending on temperature. On the other hand, no evidence of complex formation could be found by these experimental techniques for calcium, strontium and barium dodecyl sulfates, all of which are very small in solubility into water. For the former class of metal dodecyl sulfates the composition of complex was 3.5–4.0 in molar ratio of alcohol to sulfate at temperature below the melting point of alcohol, while it was 5.0–6.0 at temperature above it. The heat of complex formation above the melting point of alcohol was −40–−44 kcal/mol-sulfate. Two or three characteristic absorption bands could be found over the range 3200–3500 cm−1, suggesting that the complex formation is due to hydrogen bonding between two components.
The Kinetics and Mechanism of the Reactions of N-Sulfinylanilines with Formic Acid
Authors: Yamada Fukiko , Nishiyama Tomihiro , Emi Toshiharu 
Published: July 2006

Abstract
We have examined the kinetics of the reactions between N-sulfmylanilines and formic acid. The reactions follow this rate equation; rate=k[R–C6H4–NSO][HCOOH]. The kinetic runs were made over a wide temperature range (40–90°C) in order to obtain the values of the activation energy. The values for the reactions of N-sulfinylaniline, N-sulfinyl-p-toluidine, and N-sulfinyl-p-chloroaniline with formic acid are 14.6, 15.1, and 10.1 kcal/mol respectively. The reaction mechanism is discussed by means of their NMR spectral data.
Induced Optical Activity of Nucleic Acid-Toluidine Blue O Complex
Authors: Nakamura Tomoyasu , J. I’Haya Yasumasa 
Published: July 2006

Abstract
The absorption, circular dichroism (CD) and optical rotatory dispersion spectra of DNA–toluidine blue O complexes were observed over the visible absorption spectral region. Effect of temperature on CD was examined at the temperatures 6–86°C. For the complex of a low DNA phosphate to dye ratio, the Krönig-Kramers transform was carried out and one positive and four successive negative CD bands were resolved. It is concluded that the shorter wavelength CD bands, one positive and one negative, are due to an exciton splitting of the dye dimers and that the rest may be induced by an asymmetric environment of the DNA deoxyribose residue.
Order of Quencher Participation in Photochemistry. I. Proton Transfer from the Excited p-Hydroxybenzophenone in Mixed Solvents of Cyclohexane and Alcohols
Authors: Hoshino Mikio , Koizumi Masao 
Published: July 2006

Abstract
The change in the absorption spectrum of p-hydroxybenzophenone (HOBP) and relative quantum yields Φrel for the photoreduction of HOBP have been studied in mixed solvents consisting of cyclohexane and four kinds of alcohol. The change in absorption spectrum occurs in two steps with methanol, ethanol, and 2-propanol, suggesting the following equilibria, HOBP+S\leftrightharpoonsA, and A+S\leftrightharpoonsB (S, alcohol molecule). Φrel changes in two steps with methanol and ethanol and in one step with 2-propanol and amyl alcohol roughly in line with the spectral change. The changes in Φrel have been interpreted to be due to the deprotonation of HOBP. Φrel=1⁄(1+K[S]n) holds for them with n=5.5 for 2-propanol and n=1 for other alcohols. A linear relation holds between 1⁄(n−1)logK and Hammett’s constant of alkyl group of alcohols, suggesting that the deprotonation tendency depends upon the specific interaction between alcohol molecules. The reactivity of A-species is considered to depend largely on the dielectric nature of the solvent.
On the First Singlet and Triplet Excited States of the Lithium Molecule
Authors: Kohda Susumu , Ohno Kimio , Taketa Hiroshi 
Published: July 2006

Abstract
The first singlet and triplet excited states of Li2 are studied by the MO and VB methods. As basis, only 1s and 2s AO’s are used. In the MO description, the antibonding MO is more diffuse than the bonding MO and the difference is bigger in 1Σu+ than 3Σu+ In the VB description, splitting of the 2s orbital in the purely ionic (1Σu+) and covalent (3Σu+) wave functions does not lead to any energy lowering. An interpretation of this result is suggested. The calculated singlet-triplet separation is compared with previous calculations.
Thermal Decomposition of Ammonium Salts of Transition Metal Oxyacids. II. The Determination of the Gas Constituents Evolved by Ammonium Paramolybdate Decomposition
Authors: Park Il-Hyun 
Published: July 2006

Abstract
Gases evolved by the decomposition of ammonium paramolybdate tetrahydrate have been analyzed by means of an omegatron mass spectrometer. Only water molecules of the hydration were eliminated during the first stage of decomposition, and the final stage was not the elimination reaction of ammonia but the oxidation reaction of ammonia by Mo(VI) oxide. Between 150 and 250°C, ammonia and water were evolved in a mole ratio of roughly 2:1, corresponding to the elimination of (NH4)2O. However, the range is not clear because of the overlap of the elimination of water at the lower limit and that of nitrogen at the upper limit. At higher temperatures, a small amount of NO was observed.
Kinetics of Multidentate Ligand Substitution Reactions. XIII. Substitution Reactions of 1-(Hydroxy-4-methyl-2-phenylazo)-2-naphthol-4-sulfonic Acid (Calmagite) with Nickel (II)-Glutamate, -Aspartate, -Iminodiacetate, -Nitrilotriacetate and -Diethylenetriamine Complexes and That with the Cobalt(II)-Nitrilotriacetate Complex
Authors: Kodama Mutsuo , Sato Takami , Karasawa Sadatsugu 
Published: July 2006

Abstract
The substitution reactions of calmagite with nickel(II)-glutamate, -aspartate, -iminodiacetate, -nitrilotriacetate, and -diethylenetriamine complexes, and that with the cobalt(II)-nitrilotriacetate complex, were studied by employing the stopped-flow technique. In the calmagite reactions with the nickel(II)-glutamate, -aspartate, and -iminodiacetate complexes, the reaction products were found to be mixed-ligand complexes involving calmagite and glutamate, aspartate, or iminodiacetate anions. In these reactions, the 1 : 2 ratio complex dissociates rapidly into the 1 : 1 ratio complex first; then, the 1 : 1 ratio complex reacts slowly with the calmagite anion to form a mixedligand complex. From a comparison of the observed rate constant with that estimated on the basis of the proposed reaction intermediate, it was concluded that the latter step proceeds through the outer-sphere complex between the calmagite anion and a 1 : 1 ratio complex, and that the water-loss from the 1 : 1 ratio complex is the slowest step. In the cases of the reactions of calmagite with nickel (II)-nitrilotraicetate and -diethylenetriamine complexes, and that with the cobalt (II)-nitrilotriacetate complex, all the reaction invariably gave a metal (II)calmagite complex with a 1 : 1 composition, MD-. These reactions were found to proceed through the completely-deprotonated and divalent calmagite anions.
Kinetics of Multidentate Ligand Substitution Reactions. XIV. Substitution Reactions of Ethylenediaminetetraacetic Acid (EDTA) and N-(2-Hydroxyethyl)ethylenediamine-N,N′,N′-triacetic Acid (EDTA-OH) with Nickel(II)-Ethylenediaminemonoacetate (EDMA) and -Diethylenetriamine (Dien) Complexes
Authors: Kodama Mutsuo , Hashimoto Michinori , Watanabe Toshiyuki 
Published: July 2006

Abstract
The kinetics of the substitution reactions of EDTA and EDTA-OH with nickel(II)-EDMA and -Dien complexes were studied using the polarographic technique. The substitution reactions of EDTA and EDTA-OH with the nickel(II)-EDMA complex were found to have a common reaction mechanism. They were first-order with respect to EDTA or EDTA-OH, and also first-order with respect to the nickel (II)-EDMA complex with a 1: 1 composition; their reaction mechanism could be formulated as:
(Remark: Graphics omitted.)
The substitution reactions of EDTA and EDTA-OH with the nickel(II)-Dien complex were also studied under experimental conditions where the reaction could be treated as a pseudo-first-order reaction. The reactions were first-order with respect to the concentration of EDTA or EDTA-OH. However, their reaction rate were independent of the concentrations of the nickel(II)-Dien complex and of uncomplexed Dien. This fact was ascribed to the formation of a stable outer-sphere complex between the nickel(II)-Dien complex with a 1: 2 ratio and the EDTA or EDTA-OH anion, through which the substitution reaction proceeds.
The Extraction and Spectrophotometric Determination of Titanium(IV) with Tiron
Authors: Wakamatsu Yoshinobu , Otomo Makoto 
Published: July 2006

Abstract
A method has been described for the spectrophotometric determination of titanium(IV), which is based on the extraction of the titanium (IV)-Tiron chelate into n-butanol in the presence of 1,3-diphenylguanidinium salt. The extracted species containing titanium, Tiron, and diphenylguanidine in a molar ratio 1:2:4, has an absorption maximum at about 385 nm. The maximum extraction is obtained when the pH of the initial aqueous phase is controlled to about 3.0 to 4.0. Beer’s law is obeyed up to 25 μg titanium per 10 ml of n-butanol. The molar absorptivity of the extracted species is 1.4×10−4 at 385 nm. Molybdenum (VI) and chelating agents interfere with the determination of titanium.
Cobalt(II) and -(III) Complexes of 1,5-Dialkylpentane-2,4-diones
Authors: Yoshida Isao , Kobayashi Hiroshi , Ueno Keihei 
Published: July 2006

Abstract
Based on the spectral studies in visible, ultraviolet as well as in infrared regions, the dimeric octahedral structure was proposed for bis(heptane-3,5-dionato)cobalt(II) monohydrate, [Co(DNPM)2·H2O], bis(nonane-4,6-dionato)cobalt(II) monohydrate, [Co(DNBM)2·H2O], bis(2,8-dimethylnonane-4,6-dionato)cobalt(II) monomethanolate, [Co(DIVM)2·CH3OH], and bis(tridecane-6,8-dionato)cobalt(II) monomethanolate, [Co(DNCM)2·CH3OH]. The dimeric chelates of the type [CoL2·B], where B represented water or methanol, were stable in solid state, however, they freed the base B to form a tetrahedral monomeric complex in non-donating solvents. A red-pink solution of the cobalt(II) chelates were oxidized spontaneously in the period of a few days to give a green solution of cobalt(III) chelates of type [CoL3]. Cobalt(III) chelates of 2,6-dimethylheptane-3,5-dione (DIBM) and 2,2,6,6-tetramethylheptane-3,5-dione (DPVM) in addition to the above ligands were synthesized and their spectra were discussed in comparison with the corresponding cobalt(II) chelates.
Chemical Behavior of Carbon in High-purity Silicon in the Dissolution and Fusion of the Matrix
Authors: Nozaki Tadashi , Makide Yoshihiro , Yatsurugi Yoshifumi , Endo Yoshiyuki , Akiyama Nobuyuki 
Published: July 2006

Abstract
The behavior of carbon in high-purity silicon in the dissolution and fusion of the matrix was studied by the 11C-tracer technique. Silicon samples containing 11C, either atomistically dispersed or mainly coagulated as SiC, were prepared. In alkali dissolution, no loss of 11C was observed, and carbon originally dispersed in silicon was found to behave in a similar way to colloidal carbon under subsequent treatments. By HF–HNO3–KIO4 dissolution and succeeding KMnO4 treatment, the dispersed carbon was oxidized almost quantitatively but the SiC coagulates were not completely decomposed. In alkali fusion a part of 11C was lost. By fusion with Pb3O4-B2O3, carbon in both states was converted into CO2. The results suggest a possible application of activation analysis to the measurement of the coagulation degree of carbon in high-purity silicon.
Aroyl Arenesulfonyl Peroxides IV. The Mechanism of Carboxy-inversion of Benzoyl p-Toluenesulfonyl Peroxide
Authors: Hisada Ryuki , Minato Hiroshi , Kobayashi Michio 
Published: July 2006

Abstract
Benzoyl p-toluenesulfonyl peroxide (BTP) with 18O-labeled carbonyl oxygen and 18O-labeled sulfonyl oxygen were prepared. They were decomposed in benzene in the presence or in the absence of trifluoroacetic acid,and the phenyl p-toluenesulfonyl carbonate (PTC)-18O produced was isolated and analyzed. It was found that the carbonyl oxygen-18 of BTP was retained as the carbonyl oxygen of PTC, whereas the sulfonyl oxygen-18 of BTP was equilibrated with the peroxidic oxygen. The mechanism of the carboxy-inversion was discussed.
Heterocycles Structurally Influenced by a Side Chain. II. 7-Phenacyl-xanthopterins and 6-Phenacylisoxanthopterins
Authors: Iwanami Yasuo , Seki Taketsugu 
Published: July 2006

Abstract
Phenacyl derivatives of two naturally-occurring pteridines and their 4-amino analogues (III and V) have been synthesized for their structural study. Since these compounds are obtained by the condensation of ethyl benzoylpyruvates (II) with tri- or tetraaminopyrimidine (I), a carbon-nitrogen double bond, which is adjacent to the phenyl group of the side chain, may be expected in the ring (Remark: Graphics omitted.). However, their NMR spectra show that the double bonds of all the products are displaced onto the side chain (Remark: Graphics omitted.), the carbonyl of which is hydrogen-bonded with the secondary amino group thereby formed. This form of V makes striking contrast to alkyl isoxanthopterin-6-acetates (X), in which the corresponding double bond remains undisplaced. The intermediate products of V (IV) and V were hydrolyzed with acid or alkali into 6-methyl-isoxanthopterin (VI) and benzoic acids (VII).
Studies on Aminosugars. XXX. The Synthesis of 3′-Deoxykanamycin
Authors: Umezawa Sumio , Nishimura Yoshio , Hineno Hirokuni , Watanabe Kohei , Koike Soichiro , Tsuchiya Tsutomu , Umezawa Hamao 
Published: July 2006

Abstract
3′-Deoxykanamycin has been totally synthesized from 6-O-(2-O-benzyl-3-deoxy-3-ethoxycarbonylamino-4,6-O-isopropylidene-α-d-glucopyranosyl)-N,N′-diethoxycarbonyl-2-deoxystreptamiine and 6-azido-2,4-di-O-benzyl-3,6-dideoxy-α-dribo–hexopyranosyl chloride. It has been found that the 3′-deoxykanamycin has strong antibacterial activity not only against common bacteria but also against kanamycin-resistant bacteria.
Syntheses and Reactions of Ferrocene-Containing Polymers, VI. Polarography and Electron Transfer Equilibria of Some Ferrocene-Containing Polymers
Authors: Nakashima Toshihide , Kunitake Toyoki 
Published: July 2006

Abstract
Polarography and electron transfer equilibria of some ferrocene-containing polymers were studied in comparison with small-molecule analogs. The oxidation half-wave potentials of polyvinylferrocene and polydivinylferrocene (almost completely cyclized) in CH2Cl2 were close to those of ferrocene and [3]ferrocenophane, respectively. This is in line with structural similarity. Only one oxidation step was observed in the polarogram of triferrocenylbenzene and polyethynylferrocene, suggesting that the electronic interactions between ferrocene units are small in these compounds. Electron transfer equilibrium was observed between ferrocene units in polymer and iodine. Equilibrium constants of the [3]ferrocenophane unit were greater than those of the unbridged ferrocene unit. The ferrocene unit in polymer showed greater equilibrium constants than those of their small-molecule analogs.
Studies on Tritylated Sucrose. II. Di-O-Tritylsucroses
Authors: Otake Toshiki 
Published: July 2006

Abstract
Three isomeric di-O-tritylsucrose were isolated from a mixture of tritylated sucrose by the reaction of sucrose and trityl chloride in mole ratio 1:2 Structures of isomeric diethers were established by application of NMR to the hexa acetyl derivatives. They are recognized as 6,6′-, 1′,6-, and 1′,6′-di-O-tritylsucrose. The former two substances were crystallized as colorless prisms.
Aroyl Arenesulfonyl Peroxides. VI. Benzoyloxylation and p-Toluenesulfonyloxylation of Aromatic Compounds with Benzoyl p-Toluenesulfonyl Peroxide
Authors: Hisada Ryuki , Kobayashi Michio , Minato Hiroshi 
Published: July 2006

Abstract
Benzoyl p-toluenesulfonyl peroxide (BTP) was decomposed in benzene, toluene, chlorobenzene, nitrobenzene, or anisole in a nitrogen or oxygen atmosphere. Yields of aryl benzoates and p-toluenesulfonates were always greater in an oxygen atmosphere than those in a nitrogen atmosphere, except those with nitrobenzene. The isomer distributions of these aryl benzoates and p-toluenesulfonates were determined. The rate of decomposition in anisole was considerably greater than those in other arenes. When BTP[carbonyl-18O] was decomposed in anisole, the o- or p-anisyl benzoate formed was found to contain about equal amounts of oxygen-18 at both the carbonyl and phenoxy oxygens. On the basis of these findings the mechanisms of benzoyloxylation and p-toluenesulfonyloxylation were discussed.