bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Estimation of the Thermodynamic Properties of Organic Compounds in the Ideal Gas State. I. Acyclic Compounds and Cyclic Compounds with a Ring of Cyclopentane, Cyclohexane, Benzene, or Naphthalene
Authors: Yoneda Yukio 
Published: July 2006

Abstract
A new group-contribution method for estimating the standard enthalpy of formation, the standard absolute entropy, and the standard molar heat of organic compounds in the ideal gas state is proposed with tables of the contribution values. This method (the ABWY method) is a completely revised and enlarged version of the Anderson, Bayer, and Watson method, and it can be used with regard to a more diverse variety of compounds with a higher reliability. The neighboring effects in group-contribution methods are introduced to obtain better estimated values. The substitutions of various functional groups on aromatic rings are discriminated. Type-number corrections of the functional groups and multiple-substitution effects of halogens are also introduced; thus even heterofunctional compounds can be processed. A new concept, the quality of contribution values, is proposed to designate the qualitative reliability of the estimated physical properties. The manual procedures and tables of contribution values are given for estimating the thermodynamic properties of the compounds, as mentioned in the title, composed of C, H, O, halogens, S, and N. This method was critically compared with the Benson method in versatility and reliability.
Synthetic Studies of Laurencin and Related Compounds. V. Transformation of cis-2-Ethyl-8-formyl-3,4,7,8-dihydro-2H-oxocin-3-one 3-Ethylene Acetal into (±)-Laurencin
Authors: Masamune Tadashi , Murase Hisashi , Matsue Hajime , Murai Akio 
Published: July 2006

Abstract
Transformation of the title starting material into (±)-laurencin, which implies synthesis of the natural product, is described. The structure and configuration of synthetic intermediates are defined on the basis of the spectral evidence.
The σ-Bonded Palladium(II) Complex of (Dimethylaminomethyl)ruthenocene
Authors: Kamiyama Shin-ichi , Kimura Tetsuo , Kasahara Akira , Izumi Taeko , Maemura Mitsugi 
Published: July 2006

Abstract
The reaction between (dimethylaminomethyl)ruthenocene with lithium tetrachloropalladate(II) in the presence of sodium acetate gave di-μ-chloro-bis[2-(dimethylaminomethyl)ruthenocenyl]dipalladium(II) (2). The σ-bonded structure of 2 has been confirmed by IR analysis and the reactions of 2 with triphenylphosphine, thallium(I) acetylacetonate, and lithium aluminum deuteride. The reactions of chloro [2-(dimethylaminomethyl)ruthenocenyl](triphenylphosphine)palladium(II) with carbon monoxide and 2 with methyl vinyl ketone, phenyl vinyl ketone, and styrene have been examined. 1,2-Disubstituted ruthenocene derivatives have been obtained in higher yields than those of the corresponding ferrocene derivatives.
Improvement of Acetone Yield in the Oxidation of Propylene
Authors: Ai Mamoru , Ozaki Atsumu 
Published: July 2006

Abstract
The outstanding property of the SnO2–MoO3 catalyst in the oxidation of propylene to acetone was confirmed by tests of various oxide catalysts supported on pumice. The optimum composition was found to be SnO2-70/MoO3-30 mol % for the oxidation at from 170 to 260 °C. It was also found that this pumice-supported catalyst is sufficiently selective for the acetone formation even at a high temperature of 260 °C, and that it gives a high yield of acetone while keeping its high selectivity. The selectivity increases up to 90 mol % with an increase in the partial pressure of water vapor and with a decrease in the oxygen partial pressure. On the basis of such information, it can be said that a high yield of acetone can be obtained by the divided introduction of oxygen.
New Ring Opening Reactions of Oxiranes with Aryl Carboxylates
Authors: Funahashi Kazutoshi 
Published: July 2006

Abstract
Oxiranes reacted with aryl esters in the presence of base. The reactions of aryl carboxylates with alkyloxiranes afforded almost exclusively 1-alkyl-2-(aryloxy) ethyl carboxylates, whereas the reactions with aryloxiranes gave a mixture of 1-aryl-2-(aryloxy) ethyl carboxylates and 2-aryl-2-(aryloxy) ethyl carboxylates. Similar results were also obtained in the reaction with S-aryl thiocarboxylates and diaryl carbonates. The rate of reaction between phenyl acetate and phenoxymethyloxirane (PMO) in the presence of tributylamine (n-Bu3N) as a catalyst has been determined in the temperature range 110 to 130 °C and may be expressed by –d[PMO]⁄dt=k2[n-Bu3N]·[PMO]. The apparent activation energy calculated from the Arrhenius plots is 85.8 kj/mol. The reaction catalyzed by tributylamine is assumed to proceed through zwitter ions, n-Bu3\overset+NCH2CH(R)O− and n-Bu3\overset+NCH(R)CH2O−, which attack aryl carboxylate.
Determination of Self-diffusion Coefficient of Nickel in Nickel Sulfide
Authors: Kotani Kazuo , Ota Kenichiro , Aizawa Takemi , Fueki Kazuo 
Published: July 2006

Abstract
The self-diffusion coefficient of nickel in nonstoichiometric nickel sulfide, Ni1−δS, was measured as a function of δ, using 63Ni in the temperature range of 550–750 °C. At δ=0.028, the self-diffusion coefficient, DNi*, was expressed by the following equation:
D Ni *=3.3×10−7exp\left(−\frac73.2±9.2⁄kJ mol−1RT\ight)m2 s−1
At 550 °C and 650 °C, DNi* increased with an increase in δ from 0 to 0.04 and tended to reach the saturation point above δ=0.04.
Disproportionation of Propylene over MoO3–SiO2 Catalyst with Various Treatments
Authors: Sodesawa Toshiaki , Ogata Eisuke , Kamiya Yoshio 
Published: July 2006

Abstract
Disproportionation of propylene over MoO3–SiO2 (atomic ratio: Mo/Si=1/25) catalyst treated with HCl and aqueous ammonia was studied in the temperature range 350–600 °C under atmospheric pressure. The activity of MoO3–SiO2 catalyst extracted with aqueous ammonia remained for a long time, since most of free MoO3 was removed from the MoO3–SiO2 surface. This gave rise to increase in the selectivity for disproportionation of propylene to ethylene and butenes and decrease in the selectivity for hydrogenation, isomerization and polymerization. When MoO3–SiO2 not subjected to treatment was pretreated by H2 gas, it showed higher catalytic activity and lower selectivity for disproportionation than the one treated by N2 gas.
Synthesis and Reactions of Perylenecarboxylic Acid Derivatives, VI. Sulfonation of 3,4-Perylenedicarboximide
Authors: Nagao Yukinori , Misono Takahisa 
Published: July 2006

Abstract
The sulfonation of 3,4-perylenedicarboximide (1) with sulfuric acid has been studied. The position of the sulfo group in the monosulfonated product (2) obtained at 100 °C has been discussed on the basis of the NMR and IR spectra of 2 and the related compounds, and has been confirmed to be the 9-sulfoperylene-3,4-dicarboximide. The localized treatment of 1 by H\ddotuckel and Pople MO calculations confirmed substitution at the 9-position. Paper chromatographic analysis indicated that the reaction product was only 2 in the temperature range 60–120 °C, and the reaction rate was determined spectroscopically. The maximum formation of 2 was approximatedly 97% at 100 °C. The rate of reaction was found to be a pseudo first order process and the activation energy found to be 19.5 kcal/mol.
A Highly Stereospecific Procedure for the Transformation of Allylic Alcohols into 1,3-Dienes
Authors: Yasuda Arata , Tanaka Shin , Yamamoto Hisashi , Nozaki Hitosi 
Published: July 2006

Abstract
The title synthesis involves (1) epoxidation of allylic alcohols with t-butyl hydroperoxide in the presence of vanadium catalyst followed by trimethylsilylation, (2) specific oxirane ring opening by means of diethylaluminum 2,2,6,6-tetramethylpiperidide and subsequent desilylation producing 3-ene-1,2-diols, and (3) removal of both hydroxyl groups through bromination with a mixture of phosphorus tribromide and copper(I) bromide and the successive zinc debromination. The sequence of reactions has been extended with considerable success to the preparations of β-myrcene from nerol, trans-β-ocimene from geraniol in a specific way, and α and β-farnesenes from their biological precursors. A C12 sex pheromone of red bollworm moth has been prepared efficiently by this method with cyclododecene as a starting material.
A New Synthetic Method for Some Pyrazolo[4,3-d]pyrimidines
Authors: Takei Hisashi , Yasuda Nobuyoshi , Takagaki Hidetsugu 
Published: July 2006

Abstract
3,7-Dihydroxy- and 3-substituted 7-hydroxypyrazolo[4,3-d]pyrimidines were synthesized from diethyl oxaloacetate and ethyl acylpyruvates via ethyl 4-amino-5-oxo-2-pyrazoline-3-carboxylate hydrochloride and ethyl 5-substituted 4-amino-3-pyrazolecarboxylates, respectively.
A New Synthetic Method for Methyl Dihydrojasmonate from a Butadiene Telomer
Authors: Tsuji Jiro , Kasuga Kazuyuki , Takahashi Takashi 
Published: July 2006

Abstract
Ethyl 2-acetyl-4, 9-decadienoate, easily obtained by the palladium catalyzed telomerization of butadiene with ethyl acetoacetate, was selectively hydrogenated to ethyl 2-acetyl-9-decenoate using RuCl2 (PPh3)3 as a catalyst. Deacetylation, followed by hydrolysis produced 4-decenoic acid, which was converted into acid chloride. The AlCl3-promoted cyclization gave 2-pentyl-2-cyclopentenone, from which methyl dihydrojasmonate was prepared.
Oxidation and Reduction of MoO2–MoO3 Studied by Infrared Emission Spectroscopy
Authors: Ueno Akifumi , Bennett Carroll O 
Published: July 2006

Abstract
A sample preparation technique was developed for the study of infrared emission spectroscopy. The emission spectrum of MoO3 showed peaks at 987 and 925 cm−1 in the temperature range of 185 through 505 °C. Peak intensities were proportional to the sample weight. The background intensity in the emission spectrum was measured at 1050 cm−1 and it was also proportional to the sample weight. In order to apply emission spectroscopy to the study of reaction kinetics, the reduction of MoO3 by H2 and the oxidation of MoO2 by O2 were chosen as model reactions. These reactions were studied at 425 to 485 °C and the activation energy for the reduction of MoO3 was 43 kcal/mol and that for the oxidation of MoO2 was 38 kcal/mol. The activation energy for the formation of the terminal Mo=O bond was, however, 71.2 kcal/mol.
Preparation and Solid-phase Thermal cis-trans Isomerization of the Mixed Bis(diamine)chromium(III) Complexes of the Type [CrX2(aa)(bb)]X·nH2O
Authors: Mitra Samiran , Yoshikuni Tadatsugu , Uehara Akira , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The mixed bis(diamine)chromium(III) complexes trans- and cis-[CrX2(aa)(bb)]X·nH2O were prepared and characterized where X is chloride or bromide ion; aa and bb are different diamines selected from ethylenediamine (en), propylenediamine (pn) and trimethylenediamine (tn); and n is a number of 0 to 2. The cis-trans isomerization of the above complexes was investigated non-isothermally (derivatographically) and isothermally in the solid-phase. The isomerization was found to be one-way (trans-to-cis) and exothermic. The activation energies were estimated for dehydration or dehydration plus dehydrohalogenation (Ed) and isomerization (Ei. The intermediates mer-[CrBr3(en)(pn)]·2H2O and mer-[CrBr3(pn)(tn)]·2H2O were isolated during the isomerization of trans-[CrBr2(en)(pn)]Br·2H2O and trans-[CrBr2(pn)(tn)](H5O2)Br2, respectively. Bond rupture was proposed to be operative in the pathway of the isomerization.
Circular Dichroism Spectra of Some Transition Metal Complexes with (1R,2R)-1,2-Cyclopentanediamine
Authors: Goto Masafumi , Takeshita Michihiro , Sakai Tomoya 
Published: July 2006

Abstract
Bischelates, three isomers of dicyanocobalt(III), trans-dichlorocobalt(III), and copper(II), and a monochelate, tetracyanoferrate(II), of the title diamine were prepared, and their CD spectra were reported. Major positive components were found for Ia bands, as was to be expected for the preferred λ conformation, but minor positive components were observed for the Ib band with the trans-dianionocobalt(III) complexes. The configurational and the vicinal effects, as calculated from the CD spectra of the cis-dicyanocobalt(III) complexes, are shown to be different from those of (1R,2R)-1,2-cyclohexanediamine. The CD spectra of the Fe(II) and Cu(II) complexes are consistent with the conformational effect of the title diamine.
Autoxidation of Thujopsene in Carboxylic Acid Media. Co-preparation of Mayurone and 3-Thujopsanone
Authors: Abe Kazuo , Ito Masaaki 
Published: July 2006

Abstract
cis-(−)-Thujopsene has been autoxidized by perculation molecular oxygen through carboxylic acid solution, giving mayurone and 3-thujopsanone in fair yields. An investigation on the reaction conditions is described.
Branched-chain Sugars. XVII. Stereoselectivity in the Oxidation of Several Methyl 4,6-O-Benzylidene-2-C- or -3-C-methylene-α- and-β-d-hexopyranosides with m-Chloroperbenzoic Acid
Authors: Yoshimura Juji , Sato Ken-ichi , Funabashi Masuo 
Published: July 2006

Abstract
Stereoselectivity in the peroxy acid oxidation of methyl 4,6-O-benzylidene-3-O-methyl-2-C-methylene-α-d-ribo-hexopyranoside (1b), its 3-epimer (2b), β-anomer of 1b and 2b, methyl 4,6-O-benzylidene-2-O-methyl-3-C-methylene-α-d-arabino-hexopyranoside and its 2-epimer was examined. The results were compared with those of rigid methylenecyclohexane systems.
The Conformation of a Diastereoisomeric Pair of 2,2-Dimethyl-4-phenyl-3-pentanols
Authors: Kodama Yoshio , Nishihata Ken , Zushi Shoji , Nishio Motohiro , Uzawa Jun , Sakamoto Kazuhiko , Iwamura Hiizu 
Published: July 2006

Abstract
The conformations of a diastereoisomeric pair of 2,2-dimethyl-4-phenyl-3-pentanols were studied by means of 1H-NMR, 13C-NMR, IR, GC, and MS analyses. All of the results point to an unambiguous conclusion that these molecules are present dominantly in conformers where the t-butyl and the phenyl group lie close to each other. The generality of the phenomenon (favored gauche interaction) as well as the nature of the interactions involved were discussed in light of the conformational problems of the structurally related molecules. The presence of an attractive interaction (CH/π interaction) is suggested between an alkyl and a phenyl group, the possible importance of which in some dynamic phenomena (e.g., selectivities in certain reactions) has then been discussed on this basis.
Vibrational Spectra and Assignments for the Fundamental Vibrations of Imidazolidine-2-thione and -2-selenone
Authors: Dwarakanath K , Sathyanarayana D N 
Published: July 2006

Abstract
Infrared spectra of imidazolidine-2-thione (N,N′-ethylenethiourea, ETU) and its N,N′-deuterated (ETU-d2) and S-methylthiouronium iodides have been recorded from 4000 to 30 cm−1. Normal coordinate analyses of ETU and ETU-d2 have been made for all the fundamental frequencies, employing a Urey-Bradley potential function supplemented with valence type constants for the out of plane modes of the planar skeleton. Raman frequencies of ETU from literature have been utilised. The results of the vibrational analyses are discussed in relation to the group frequencies in structurally related molecules and frequency shifts on deuteration and S-methylation. The normal coordinate treatment is also performed for the planar vibrations of imidazolidine-2-selenone (N,N′-ethyleneselenourea, ESU) to propose assignments for ESU and so also to support the assignments of ETU.
Preparation of Fortamine and 6-epi-Purpurosamine B from Fortimicin B
Authors: Sano Hiroshi , Sakaguchi Tomoko , Mori Yasuki 
Published: July 2006

Abstract
Benzyl alcoholysis and hydrolysis of tetrakis-N-(benzyloxycarbonyl)fortimicin B and further transformation of the solvolysis products are described. Several derivatives of 6-epi-purpurosamine B and fortamine potentially useful for the synthesis of fortimicin analogs are presented.
A Molecular Orbital Study on the Nucleophilicity and the Electrophilicity of Free Radicals in Abstraction Reactions
Authors: Shinohara Hiroyuki , Imamura Akira , Masuda Takahiro , Kondo Masaharu 
Published: July 2006

Abstract
The polarities (nucleophilicity and electrophilicity) of free radicals in abstraction reactions were studied by the comparison of the stabilization energies due to delocalization of electrons (SEDE) between a radical and a substrate. The stabilization energies were calculated by the CNDO/2 method for several substrate–radical systems. For the reactions of the methyl radical with chlorinated methanes, the nucleophilicity of the radical was well interpreted by the SEDE from the radical to the substrate. Similarly, the nucleophilicity of the hydrogen atom in chlorine abstraction from chlorinated methanes was indicated by the SEDE from the hydrogen atom to the substrate. In an electrophilic reaction such as hydrogen abstraction by the methyl radical from aliphatic hydrocarbons, the activation energy was found to decrease linearly with an increase in the SEDE from the substrate to the radical. This result is consistent with the electrophilic tendency of the reaction. The SEDE calculated for the reactions of a radical with a series of substrate thus indicates the polarity of the free radical in the abstraction reactions.
An Analysis of the UV, ORD, and CD Bandshapes of the DNA–Acridine Orange Complex by the Linear Response Polarizability Theory
Authors: Ito Hirotoshi , I’Haya Yasumasa J 
Published: July 2006

Abstract
The linear response polarizability theory of the spectral bandshapes is applied to the numerical analysis of the UV, ORD, and CD spectra of the DNA–Acridine Orange complex by using various models of conformation. In all calculations, we make use of an infinite orders approximation for the intermonomer electronic interaction, since convergence of the Dyson-type series for the polymer polarizability tensor sometimes becomes seriously slow, in particular in such case that the transition moments of a constituent monomer such as Acridine Orange are quite large. It is found that among the various outside-stacking models, a dimer-pairs repeating sequence model newly proposed leads to reasonable results for the UV, ORD, and CD spectral bandshapes.
Asymmetric Transformation of Alanine via Optically Labile Imidazolines
Authors: Shibata Saizo , Matsushita Hajime , Kato Kunio , Noguchi Masao , Saburi Masahiko , Yoshikawa Sadao 
Published: July 2006

Abstract
Hydrolysis of an imidazoline derived from (S)-alanine and (S)-2-(aminomethyl)pyrrolidine afforded (R)-alanine in the optical yield of 93.8% (e.e.). The asymmetric transformation was explained on the basis of preferential crystallization of one epimer followed by epimerization of the other epimer in a solution. It was found that the epimerization was catalyzed by amines. (2S)-N-isopropyl-2-aminopropylamine was also examined as a diamine component of imidazolines.
Study of Metal-Polycarboxylate Complexes Employing Ion-selective Electrodes. II. Stability Constants of Copper(II) Complexes with Poly(acrylic acid) and Poly(methacrylic acid)
Authors: Yamashita Fumitaka , Komatsu Tsuyoshi , Nakagawa Tsurutaro 
Published: July 2006

Abstract
The copper(II) complex formation with poly(acrylic acid) and poly(methacrylic acid) in aqueous solution was studied by potentiometric titration employing glass and copper(II) ion-selective electrodes. The values of the equilibrium constants of the complex formation and the stability constants were estimated in various degree of neutralization. Since the concentration of free copper(II) ions could be determined by employing the copper(II) ion-selective electrode, the concentrations of two complex species, involving one and two carboxylato groups, were determined from stoichiometric equations. The equilibrium and stability constants of the complexes obtained were observed to pass through peaks with increase in the degree of neutralization. The order of magnitude of the equilibrium constant of the polyacrylate complex was larger than that of the polymethacrylate complex.
Formation of Benzyl Radicals by Pulse Radiolysis of Benzyltriphenylphosphonium Chloride in Aqueous Solutions
Authors: Horii Hideo , Fujita Shinichi , Mori Toshiaki , Taniguchi Setsuo 
Published: July 2006

Abstract
The reaction of benzyltriphenylphosphonium ion (PhCH2P+Ph3) with eaq− has been studied. The benzyl radical and triphenylphospine are formed by the reaction: PhCH2P+Ph3+eaq−→PhCH2·+Ph3P, with the rate constant (2.7±0.3)×1010 M−1 s−1. The benzyl radical decays in a bimolecular reaction with 2k=(2.7±0.4)×109 M−1 s−1.
Peri Interaction in Naphthalene Ketones
Authors: Kubo Masao , Sato Takeo 
Published: July 2006

Abstract
Peri interaction in several naphthalene ketones was investigated using the carbon-13 NMR, IR, and UV spectra. The carbonyl carbon resonances for 7H, 14H-cycloocta[1,2,3-de:5,6,7-d′e′]dinaphthalene-7,14-dione and its 7-oxa analog were found to be shifted upfield by 27 and 24 ppm respectively compared with those of model compounds. The anomalous shift for the former was attributed to π-orbital compression, which inhibited the polarization of carbonyl groups because of a forced parallel geometry, while the latter was attributed to field effects. The conclusion was supported by UV and IR data.
A New Method for the Synthesis of 2-Substituted 2-Buten-4-olide via α-Substituted β-Phenylthio-γ-butyrolactone
Authors: Watanabe Mikio , Shirai Kozo , Kumamoto Takanobu 
Published: July 2006

Abstract
The addition reaction of lithium benzenethiolate to 2-buten-4-olide in the presence of aldehydes and ketones afforded α-substituted β-phenylthio-γ-butyrolactones (4a–f). The dehydrosulfenylation of 4a–d proceeded smoothly to give 2-substituted 2-buten-4-olide by the reflux of α-substituted β-phenylsulfinyl-γ-butyrolactone, which was prepared by the oxidation of 4a–d, in the presence of triethylamine.
The Crystal and Molecular Structure of (±)-2-Methylamino-4,5-bis(p-chlorophenyl)-4-hydroxy-4H-imidazole
Authors: Takayanagi Hiroaki , Ogura Haruo , Matsuzaki Keinosuke , Kitajima Koji , Nishimura Tamio 
Published: July 2006

Abstract
The crystal and molecular structure of (±)-2-rnethylarnino-4,5-bis(p-chlorophenyl)-4-hydroxy-4H-imidazole has been determined by the single-crystal X-ray diffraction method. The crystals are monoclinic with space group P21/c, cell dimensions: a=14.872(5), b=9.216(7), c=12.945(11) Å, β=99.53(5)°, and Z=4. The structure was determined by the symbolic addition method and refined by the least-squares method to give the final R factor of 0.072 for 1616 non-zero reflections.
Monolayer Studies of Chiral and Racemic 12-Hydroxyoctadecanoic Acids
Authors: Tachibana Taro , Yoshizumi Tokiko , Hori Kayako 
Published: July 2006

Abstract
The monolayer properties of chiral and racemic 12-hydroxyoctadecanoic acids (12HOA) have been studied. Both acids showed, in each pressure-area isotherm, a pressure plateau. This was interpreted as a two-dimensional phase transition region: from the expanded monolayer composed of bent chain molecules with both the hydroxyl and carboxyl groups attached to the water surface, to the condensed monolayer composed of straight chain molecules oriented steeply to the water surface. It was suggested by measuring infrared spectra of the collapsed films and the built-up films that the condensed monolayer involves intermolecular hydrogen bonds. Differences between (R)- and dl-12HOA were found in the plateau pressure and its temperature dependence leading to the transition energy. These results were attributed to the formation of a recemic molecular compound during condensation of monolayers of dl-12HOA, prior to collapse, followed by a different manner of hydrogen bonding. Electron microscope observation gave strong evidence for the two-dimensional racemic compound formation. On the basis of these results and the X-ray diffraction data, molecular packing models in the condensed monolayers were proposed.