bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Crystal and Molecular Structure of Perchloro-(3, 4, 7, 8-tetramethylene-tricyclo[4.2.0.02,5]octane), C12Cl12
Authors: Furusaki Akio 
Published: July 2006

Abstract
The stereochemistry of perchloro-(3, 4, 7, 8-tetramethylene-tricyclo[4.2.0.02,5]octane) has been studied by three-dimensional X-ray crystal analysis. The crystal of this compound is triclinic, with one molecule in a unit cell with the dimensions; a=9.35, b=7.45, c=8.44 Å, α=111.8°, β=117.6°, and γ=96.0°. The space group is P1 or P\bar1, the latter being assumed throughout the present study. The crystal structure was elucidated by the minimum function method. The atomic parameters thus obtained were refined by the least-squares method, using the diagonal-matrix approximation. Each conjugated system in a molecule is nearly planar in spite of very close contact between the two adjacent dichloromethylene groups of the same system, the nearest approach occurring between the chlorine atoms with a distance of 3.28 Å. The whole molecule has a rather simple chair-like form, with an approximate symmetry of C2h.
Proton Magnetic Resonance of Solid 1,1,1,2-Tetrachloro-2-methylpropane
Authors: Koide Tsutomu , Oda Tsutomu 
Published: July 2006

Abstract
The molecular motion in the crystal lattice of 1, 1, 1, 2-tetrachloro-2-methylpropane was studied, by proton magnetic resonance absorption measurements, over the temperature range between 30°C and −190°C. The absorption-line witdhs changed at −62°C. The second moments remain almost constant, about 5 gauss2, between from −63°C to about −150°C, whereas above −62°C the values fall suddenly to 0.5 gauss2. From the analysis of the proton second moment, it was found that, in the high-temperature phase, the molecules rotate almost freely in the crystal lattice, while in the low-temperature phase, the major molecular motion is the rotation of the methyl groups about the C–CH3 bonds in the molecule.
The Spectrophotometric Determination of Perchlorate Ions by Solvent Extraction with Crystal Violet
Authors: Uchikawa Sumio 
Published: July 2006

Abstract
A micro quantity of perchlorate ions is extracted into chlorobenzene with crystal violet. The absorbance maximum of the extract in the organic layer is found to be at 595 mμ. The maximum and the constant extraction was obtained in the pH range of 2–7. In order to ascertain the optimum conditions for the determination of perchlorate ions, various factors have been studied: the effects of the concentration of the dyestuff, the pH of the solution, the standing time of the solution, the times of the extraction, and the presence of diverse ions. The recommended procedure for the calibration curve is as follows: Two milliliters of a crystal violet solution (1×10−3 m), 5 ml of a potassium phosphate buffer solution (1 m, pH 5.8), and various volumes (0–10 ml) of a standard perchlorate solution (2×10−5 mol/l) are mixed. The mixed solution is diluted to 25 ml with water. An aliquot (10 ml) of the solution is then poured into a separatory funnel and is shaken for 5 min with 10 ml of chlorobenzene. The absorbance of the organic layer is measured at 595 mμ against the reagent blank solution. Beer’s law is obeyed in the perchlorate range of 10−7–8×106 mol/l in the aqueous layer before the extraction. Considerable amounts of chloride, iodate, and sulfate ions do not interfere.
Solvent Extraction and Spectrophotometric Determination of the Pertechnetate Ion with Methyl Violet
Authors: Fujinaga Taitiro , Koyama Mutsuo , Kanchiku Yoshihiko , Tsurubo Shigeo 
Published: July 2006

Abstract
A spectrophotometric method of determination of TcO4− subesquent to solvent extraction with methyl violet was investigated. Methyl violet which has a molar extinction coefficient of about 2×105 at 585 mμ in a neutral aqueous solution was found to be extractable with TcO4− into monochlorobenzene. The absorption maximum of the dye in the organic layer after extraction shifts to 595 mμ, at which point the absorbance is proportional to the amount of TcO4− added to the aqueous solution. The effect of the pH on the absorbance of organic layer was very small as long as the absorbance was measured against the reagent blank as a reference. Over the wide range of pH values from 2 to 10, an approximately constant absorbance was obtained for a fixed amount of TcO4−. Effects of diverse ions were also examined. Alkali salts of phosphate, borate, citrate, and tartrate have little effect on the absorbance of the organic layer, whereas perchlorate and perrhenate seriously interfere. When the extraction efficiencies of TcO4− were measured using 95mTc and 97mTc as tracers, they were found to be quantitative, even at a concentration as low as 10−12m.
Separation of the Stereoisomers of Di-s-butyl Ether
Authors: Taniguchi Hiroaki , Iriuchijima Makoto , Komatsu Youji 
Published: July 2006

Abstract
d-Di-s-butyl ether was prepared by the reaction of d-s-butyl-alcoholate and optically inactive di-s-butyl sulfate, followed by displacement chromatography. With the same chromato-graphic technique, meso- and rac-di-s-butyl ether were separated from the commercial di-s-butyl ether.
Untersuchung der freien Fettsäuren, der freien Sterine, der Sterinester und der Glyzeride im Regenwurm (Lumbricus Spencer)
Authors: Naya Yoko , Kotake Munio 
Published: July 2006

Abstract
Aus den beiden Ätherextrakten von getrocknetem und frischem japanischen, gewöhnlichen Regenwurm (Lumbricus Spencer) wurden die freien, niedrigen und höhern Fettsäuren isoliert, und darin wurden neben gewöhnlichen, geradzahlig-gesättigten und ungesättigten Fettsäuren, auch ungeradzahlig-gesättigte und isomere Verbindungen gefunden. Mit Hilfe der Gaschromatographie wurde das Fettsäuremethylestergemisch in seine Komponenten zerlegt und die Strukturzusammensetzungen jener Komponenten wurden mittels Mass- und NMR-Spektren identifiziert. In den freien Sterinen, die wir isoliert haben, wurden neben Cholesterin, auch Brassicasterin gefunden. Provitamin D oder Δ5,7-Sterin wurde durch UV Absorption in rohen Sterinen nicht aus frischem Regenwurm, sondern aus getrocknetem Wurm (etwa 1.7%) entdeckt. Beim Lumbricus Spencer wurde Ergosterin, das beim Lumbricus terrestris (F. Bock und F. Wetter, Z. Physiol. Chem., 256, 55 (1938)) entdeckt wurde, nicht gefunden. Aus je getrocknetem und frischem Regenwurm wurden die Sterinester isoliert. Das Fettsäuregemisch, das man beim Verseifen der Sterinester gewinnt, besteht aus n-C16, n-C17 und n-C18 Fettsäuren. Die Sterine aus den Sterinestern setzen sich aus Cholesterin und Brassicasterin zusammen. Die Glyzeride wurden aus je getrocknetem und frischem Regenwurm isoliert. Die Fettsäuren aus den Glyzeriden waren die gleichen Komponenten wie die freien Fettsäuren.
The Radiation-induced Addition Reactions of Ethers and Alcohols to Perfluoropropene
Authors: Muramatsu Hiroshige , Inukai Kan , Ueda Teruo 
Published: July 2006

Abstract
The radiation-induced addition reactions of ethers and alcohols to perfluoropropene were studied. Mainly the 1:1 adducts were obtained in excellent yields, but in the addition of di-ethyl ether and dioxane the 1:2 adduct with a symmetrical structure was produced along with the 1:1 adduct. The ethers containing the perfluoropropenyl group were prepared by the dehydrofluorination of the corresponding 1:1 adduct. From the proton and fluorine NMR spectra, the attacks of the α-ethereal and α-hydroxyalkyl radicals were found to occur exclusively on the difluoromethylene carbon. The relative reactivities of ethers and alcohols were determined by competitive reaction.
The Conjugative Effects of Thia, Sulfinyl and Sulfonyl Groups on the Dissociation of p-Substituted Phenols
Authors: Oae Shigeru , Yoshihara Masakuni , Tagaki Waichiro 
Published: July 2006

Abstract
Several di- or tetramethyl substituted derivatives of bis-(4-hydroxyphenyl)sulfides, sulfoxides and sulfones were newly prepared and their acid dissociations, UV and IR spectra were reinvestigated. Essentially no steric inhibition was observed in the 3-d orbital resonance with the sulfinyl and the sulfonyl groups in both the acid dissociations and the UV spectra of the substituted phenols. However, a small but noticeable steric inhibition by ortho methyl groups was observed with the mercaptophenol.
Thermo-Analytical Investigation of Phase Equilibria in the Al2O3-SiO2 System
Authors: Horibe Toshiyasu , Kuwabara Senzo 
Published: July 2006

Abstract
The phase equilibrium relation of the Al2O3-SiO2 system was thermo-analytically investigated using a molybdenum resistance furnace with an argon atmosphere and a tungsten-tungsten 26% rhenium thermocouple (supplementary experiments were also made), and the phase diargam for the high aluminous region was presented. The composition of mullite with the highest melting point is 2Al2O3·SiO2 or very close to that value, and the mullite of the composition melts in-congruently at 1890±5°C, giving a liquid with a composition slightly less in Al2O3 content than that of the mullite. Other investigators’ results were interpreted on the basis of the results of the present investigation. In the present experiment an “unstable” growth of corundum was frequently observed.
Studies on the Liquid-Liquid Partition Systems. VI. Solvent Extraction Study of the Dissociation of Sulfurous, Selenious and Tellurous Acids in Acid Perchlorate Media
Authors: Sekine Tatsuya , Iwaki Hidehiko , Sakairi Mitsuo , Shimada Fumitake , Inarida Mariko 
Published: July 2006

Abstract
Liquid-liquid distribution behavior of sulfur(IV), selenium(IV) and tellurium(IV) in acid perchlorate media was studied at 25°C. The distribution of sulfur(IV) into carbon tetrachloride was determined by iodometry and that of selenium (IV) into methylisobutyl carbinol or of tellurium(IV) into hexane containing trioctylphosphine oxide was determined by radiometry. The changes in the distribution ratio caused by the changes in the hydrogen ion concentration were explained in terms of the distribution of sulfurous, selenious or tellurous acid as the non-charged form into the organic phase and the dissociation of these acids in the aqueous phase. The distribution constants as well as the dissociation constants of these acids were determined by a graphical method. In acid perchlorate media, sulfurous and selenious acids exist as neutral and mononegative species while tellurous acid exists as monopositive, neutral and mononegative species, and the neutral species exists only in a narrow hydrogen ion concentration range.
Electronic Spectra and Electronic Structures of Benzonitrile N-Oxide and Its Derivatives
Authors: Yamakawa Masumi , Kubota Tanekazu , Akazawa Hideko , Tanaka Itaru 
Published: July 2006

Abstract
The electronic spectra of 2,6-dimethylbenzonitrile N-oxide and its some derivatives were recorded in n-heptane and were compared with those of benzonitrile and phenylacetylene. The analyses of the electronic spectra of aromatic nitrile N-oxides were done by the following procedures. First, simple molecular orbitals (SMO) of benzonitrile and phenylacetylene were calculated using some parameters determined by the use of the overlap integrals and valence state ionization potentials. Then, by comparing the eigenvalues of the SMO thus obtained with the observed spectra the spectroscopic exchange integrals have been obtained for 1A1 and 1B1 bands, where interactions between two configurations were taken into consideration for the 1B1 bands. The SMO of benzonitrile N-oxide was next calculated on reference to the physicochemical nature of aromatic nitrile N-oxides studied before. The parameters were chosen so as to fit with the observed values of dipole moments of benzonitrile N-oxide and its some methyl derivatives. Electronic spectra of the nitrile N-oxides were then analyzed using the above SMO’s and spectroscopic exchange integrals. The substituent effect on the electronic spectrum of benzonitrile N-oxide was also discussed by the similar treatment. Characteristic strong band appearing in the near UV region was assigned to the 1A1 band having a change transfer (CT) nature, where the CT from the oxygen atom to the residual conjugated system makes a larger contribution than that of the reverse direction. In addition, the physicochemical nature and reactivity of nitrile N-oxides were discussed on the basis of their molecular diagrams, which were obtained from the SMO’s mentioned above.
A New Determination Method of Relative Rate Constants for Reactions with OH-radicals in Radiolysis of Aqueous Solutions
Authors: Morita Makio , Fujimaki Masao 
Published: July 2006

Abstract
Radioactivity of water increased linearly with dose when aqueous solution of 3H-formate (2 μCi/ml and 2×10−8 m) was irradiated with γ-rays in the presence of oxygen. The increase of the radioactivity was found to be reciprocally proportional to the non-labeled formate concentration where the amount of 3H-formate was kept invariable. Addition of ferrocyanide and 2-propanol, effective OH-radicals scavengers, depressed the radioactivity increase to near zero. These facts show that the abstraction of tritium from 3H-formate by OH-radicals causes the increase of the radioactivity of water. A competition method to measure relative rate constants for reactions with OH-radicals was deviced on the present results. Some values obtained by this method were in agreement with published data.
Intramolecular Hydrogen Bonding in Monoterpene Alcohols Containing π-Electronic System
Authors: Shishibori Tsuyoshi 
Published: July 2006

Abstract
The nature of intramolecular hydrogen bonding in diastereoisomeric pairs of 10-nor-8-oxomenthols (VIII and IX) and 10-nor-8-oxocarvomenthols (X and XI) has been studied by infrared spectroscopy. It was found that 10-nor-8-oxoneomenthol (IX) contains the OH···O type intramolecular hydrogen bond, while 10-nor-8-oxomenthol (VIII) contains the OH···π interaction in addition to the OH···O hydrogen bond. 10-Nor-8-oxocarvomenthols (X and XI) were internally unbonded. In addition, the extent and the limitation of the intramolecular OH···π interaction has been investigated for the diastereoisomeric pairs of a series of p-menth-8-enols: p-menth-8-en-4-ols (I and II), isopulegols (III and IV), dihydrocarveols (V and VI), and trans-β-terpineol (VII). Thus, the hydroxyl group in α- or β-unsaturated alcohols I, II, III and IV was found to be internally bonded to the π-electrons on the double bond; the other isomers are internally unbonded.
The Synthesis of 4-Hydroxyfuro[2′,3′:7,8]coumarins 5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one
Authors: Kawase Yoshiyuki , Nanbu Mutsumu , Yanagihara Hirokazu 
Published: July 2006

Abstract
4-Hydroxyfuro[2′,3′:7,8]coumarin (16) and its 3-phenyl (10) and 3-(2-methoxyphenyl) (11) derivatives were prepared from the corresponding 4-hydroxy-5-benzofuranyl ketones (15, 8a and 8b) by the action of ethyl carbonate and sodium. The furocoumarin 11 thus obtained was converted to 5H-benzofuro[3,2-c]furo[2,3-h][1]benzopyran-5-one (18), a compound having a new pentacyclic ring system, by the demethyl-cyclization with pyridine hydrochloride, hydroiodic acid or aluminum chloride. The attempted preparation of these compounds through their dihydro compounds is also described; 2,3-dihydro-4-hydroxybenzofuran (1) was acylated with phenylacetic acid, with 2-methoxypheny lace tic acid or with 2,4,5-trimethoxyphenylacetic acid by the action of polyphosphoric acid to give a mixture of the 5- and 7-acylated compounds (3 and 2), and the formers were converted to the corresponding 4″,5″-dihydrofuro[2″,3″:7,8]isoflavones (6), 4″,5″-dihydro-2-methylfuro-[2″,3″:7,8]isoflavones (4) and 4′,5′-dihydro-4-hydroxyfuro[2′,3′:7,8]coumarins (7). The 2,3-dihydro-4-hydroxy-5-benzofuranyl benzyl ketone (3a) and the dihydrofuroisoflavones (4a and 4b) were also obtained by the catalytic reduction of the corresponding furo-compounds.
Synthetic Studies of α-Tocopherol. III. Synthesis of Phytone
Authors: Ichikawa Takehiko , Kato Tetsuya 
Published: July 2006

Abstract
Phytone (XI), an important intermediate in the preparation of α-tocopherol, was synthesized by a selective Wittig reaction between geranyltriphenylphosphonium halide (VII) and the aldehyde group of 2-methyl-6-oxoheptanal (VIII), followed by the hydrogenation of the product. VIII was prepared from 1,3-dimethyl-1-cyclohexene (V) by ozonolysis and reductive decomposition. V could not be obtained in a pure state by the dehydration of 2,6-dimethylcyclohexan-1-ol (II), presumably because of the isomerization of the intermediate carbonium ion. The pyrolysis of the acetate of II (III) was found to give pure V. That the hardly-pyrolizable stereoisomer of III was cis,cis-2,6-dimethylcyclohexyl-1-acetate (VI) is consistent with the cis-elimination mechanism.
The Partial Resolution of Racemic α-Alanine through the Cobalt(III) Complexes of Optically Active Aspartic or Glutamic Acid
Authors: Shibata Muraji , Nishikawa Hiroaki , Hosaka Kinya 
Published: July 2006

Abstract
When a hundred per cent excess of racemic α-alanine was reacted, in the presence of activated charcoal, with a reaction mixture of tricarbonatocobaltate(III) and l-asparate, water-insoluble β-tris(alaninato) cobalt (III) was precipitated. The recovery of alanine from this triscomplex showed a partial resolution; the d form of alanine was preferentially complexed, and the optical purity of the alanine recovered was about 38%. Spectroscopic measurements (absorption, ORD and CD) showed that the predominantly-existing species in the above reaction mixture was the (−)-[Co CO3(l-asp)2]3− anion, and that the reaction of this complex anion with racemic alanine led to the predominant formation of β(−)-[Co(d-ala)2(l-ala)] (the (−) sign refers to the sign of the Cotton effect in the first absorption band region). Similar experiments were carried out with d-aspartate and l-glutamate in place of l-aspartate. Through all the experiments, we have found that the complexes which are effective for the resolution of racemic alanine and the product or tris(alaninato) cobalt (III) have the same sign of the Cotton effect in their first-band regions.
Stability Constants of Some Uranyl Complexes
Authors: Ramamoorthy S , Santappa M 
Published: July 2006

Abstract
Complexes of uranyl ion with benzoic, phenylacetic, phenoxy-acetic, thiomalic and itaconic acids were studied by pH titration method at 31±0.1°C. A 1 : 1 complex is formed in all the cases in the pH range 2.5–3.5 and their stability constants are reported.
Kinetics of Multidentate Ligand Substitution Reactions. II. Substitution Reactions of BT with Nitrilotriacetato Nickelate(II) Chelate and with Ethylenediaminetetraacetato Nickelate(II) Chelate
Authors: Kodama Mutsuo , Sasaki Chifumi , Murata Mitsuko 
Published: July 2006

Abstract
This paper reports a spectrophotometric study of the solution equilibria and the kinetics of the substitution reaction of Eriochrom Black T (BT) with nickel(II)-NTA and with nickel (II)-EDTA chelates. In solutions of pH 8.50–9.50 containing a large excess of uncomplexed NTA over BT and nickel (II)-NTA chelate, BT forms only 1-to-1 normal chelate, NiD−, with the nickel(II) ion, the stability constant of which is 1020.8(μ=0.30). Kinetically, the ligand-exchange reaction of BT with the nickel (II)-NTA chelate was found to proceed through the following two simultaneous reaction paths and to be much faster than that with the nickel(II)-EDTA chelate,
2i) &  NiX^-+HD^2-\ightleftharpoonsNiD^-+HX^2- ii) & & HD^2-\oversetrapid\ightleftharpoonsD^3-+H^+
& rapid\upharpoonleft\downharpoonright& &  NiX^-+D^3-\ightleftharpoonsNiD^-+X^3-
&  NiX_2^4- & & rapid\upharpoonleft\downharpoonright
& & & NiX_2^4- rate-determining step
where NiX−, NiX24−, HD2−, and D3− represent Ni(II)-NTA chelate of 1-to-l composition, Ni(II)-NTA chelate of 1-to-2 composition, doubly deprotonated BT anion and completely deprotonated BT anion, respectively. The substitution reaction of BT with nickel(II)-EDTA chelate was found to proceed mainly through the following reaction path,
& HD^2-\oversetrapid\ightleftharpoonsD^3-+H^+ & NiY^2-+D^3-\ightleftharpoonsNiD^-+Y^4-
& &rate-determining step
and the contribution of the following reaction to the whole reaction is negligible at pH 9.00–10.50.
NiY^2-+HD^2-\ightleftharpoonsNiD^-+HY^3-
Studies on Photo-polarography. I. Polarographic Behavior of Trioxalato-ferrate(III) Ion under Ultraviolet Irradiation
Authors: Yamashita Kazuo , Imai Hideo 
Published: July 2006

Abstract
The polarographic behavior of trioxalatoferrate(III) ion under irradiation of ultraviolet light was studied. Trioxalatoferrate(III) was photo-chemically reduced in the bulk and the polarographic reduction current changed into the oxidation one, which showed a highly kinetic characteristic. The current-time curve during one drop growth of the dropping mercury electrode under irradiation was analyzed, and the rate constant of the photo-chemical reaction (kν) was evaluated. The apparent value given as kν′=I0εkν was 0.35 cm−1, where I0 being the intensity of the incident light and ε the extinction coefficient. The time dependence of the photopotential was elucidated on the basis of the Nernst equation. The possible photonometric determination of dissolved oxygen was suggested from the effect of dissolved oxygen on the half-life of the photo-chemical reaction.
Some Reactions of N-Haloamidines
Authors: Haruki Eiichi , Inaike Toshihiro , Imoto Eiji 
Published: July 2006

Abstract
The reactions of a variety of N-haloamidines with silver oxide, sodium ethoxide, thiourea derivatives, and phenols are described. In these reactions, N-phenyl-N′-chlorobenzamidine gave diphenylcarbodiimide, benzimidazole, N-amidinobenzamidine and 2,4-diphenylthiadiazole respectively, while the other N-haloamidines afforded the corresponding products. The mechanistic implications of these reactions are discussed.
Syntheses of Some Heterocyclic Compounds from α-Benzoylimino-benzyl Cyanide and Related Compounds
Authors: Fujimori Masahiro , Haruki Eiichi , Imoto Eiji 
Published: July 2006

Abstract
The reaction of α-benzamidobenzyl cyanide (I) with thionyl chloride and pyridine in benzene gave α-benzoyliminobenzyl cyanide (II) in a 52% yield. II is a novel compound which can react readily with nucleophilic reagents, such as alcohols, mercaptans and amines. The reaction of II with ethyl-mercaptan and with alcohols gave α-ethylthio-α-benzamidobenzyl cyanide and α-alkoxy-α-benzamidobenzyl cyanide respectively. Furthermore, II reacts with bifunctional nucleophilic reagents to form heterocyclic compounds. The reaction of II with hydrazine and with hydroxylamine afforded 3,5-diphenyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-oxadiazole respectively.