bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Dipole Moments of Diphenyl Sulfide, Sulfoxide, Sulfone, and Their Derivatives
Authors: Toshiyasu Yoshio , Taniguchi Yoshio , Kimura Ko , Fujishiro Ryoichi , Yoshihara Masakuni , Tagaki Waichiro , Oae Shigeru 
Published: July 2006

Abstract
The electric dipole moments of diphenyl sulfide, sulfoxide, and sulfone and their derivatives were determined in benzene solutions at 25°C. The observed moments are used to estimate the mesomeric moments on the assumption of the vector addition of group moments. The mesomeric moments of the phenylmercapto, phenylsulfinyl, and phenylsulfonyl groups are estimated to be −0.12, 0.10, and 0.44 D, respectively. The steric effect of ortho-substituents is also discussed on the basis of the dipole moment data.
Secondary Structure of Poly-l-arginine and Its Derivatives
Authors: Hayakawa Tadao , Kondo Yoshiyuki , Yamamoto Hiroyuki 
Published: July 2006

Abstract
The conformations of poly-Nω,ω′-dicarbobenzyloxy-l-arginine, poly-Nω-carbobenzyloxy-l-arginine, and poly-L-arginine hydrobromide were studied by means of their infrared spectra (IR), X-ray photographs, optical rotatory dispersions (ORD), and circular dichroisms (CD). The presence of the α-helical conformation in poly-Nω,ω′-dicarbobenzyloxy-l-arginine and poly-Nω-carbobenzyloxy-l-arginine was confirmed by X-ray photographs and by their IR spectra. The ORD and the CD curves of these polymers were found to be characteristic of the α-helical conformation. It was also found that these polypeptides have a random coil conformation in trifluoroacetic acid. In the (2-chloroethanol : trifluoroacetic acid) solvent system, the typical helix-coil transition of poly-Nω-carbobenzyloxy-l-arginine was observed at 20–30% trifluoroacetic acid. The ORD and the CD curves of poly-l-arginine showed that the polymer took a random coil structure in the pH range from 2.7 to 11.0. However, when the pH is increased from 11.0 to 11.5, the spectra gradually change into the α-helix structure. Moreover, the polypeptide predominantly took the α-helix structure at pH 12.5. From the ORD and CD data, the polypeptide can be considered to have a right-handed α-helix conformation.
Reactions of Cycloalkanone Oxime p-Toluenesulfonates
Authors: Sato Tadashi , Wakatsuka Hirohisa 
Published: July 2006

Abstract
The reactions of cyclohexanone and cyclopentanone oxime p-toluenesulfonates were studied. It was found that cyclohexanone oxime p-toluenesulfonate (IIIa) afforded a tetrahydroazepine derivative (Va), while cyclopentanone oxime p-toluenesulfonate (X) afforded δ-valerolactam p-toluenesulfonate (XIII), when both compounds were heated in benzene.
The Reaction of Haloferrocenes with Copper (I) Salts in Pyridine
Authors: Sato Masaru , Ito Takehiko , Motoyama Izumi , Watanabe Ken-ichi , Hata Kazuo 
Published: July 2006

Abstract
The halogen exchange reaction of haloferrocene series with copper(I) salts (halide, cyanide) in an organic base was studied in comparison with that of the halobenzene series, which is regarded as a kind of nucleophilic substitution. Chloro-, bromo-, and cyanoferrocene were all obtained from iodoferrocene by this reaction in good yields. The reactivity of the ferrocene series was much higher than that of the benzene series. The order of the reactivity of halogen, I&gt;Br&gt;Cl, was similar to that of the benzene series. On the other hand, the substituent effects in the comparative reactivity of 1’-substituted-1-chloroferrocene with copper(I) cyanide was observed to be as follows: Et&gt;H&gt;Cl&gt;Ac. This order in the ferrocene series was opposite to that in the p-substituted bromobenzene series: CN&gt;Ac&gt;Br&gt;H&gt;Me. In view of the electrophilic tendency in the ferrocene series and its high reactivity, the reaction mechanism is discussed.
Studies of the Precipitation of Humic Acid by Cationic Polyelectrolytes
Authors: Kumanomido Hiroshi 
Published: July 2006

Abstract
In order to elucidate the mechanism of the precipitation of humic acid by two cationic polyelectrolytes, the n-butylamine-epichlorohydKin condensation polymer (BECP) and the cyclohexylamine-epichlorohydrin condensation polymer (CECP), electrophoresis and conductometric titration were made in conjunction with precipitation experiments in various concentrations of humic acid with an optimum dosage of cationic polyelectrolyte. The results of these experiments indicated that a cationic polyelectrolyte precipitates the humic acid by combining stoichiometrically with the negatively-charged groups of the humic acid. A possible mechanism for the precipitation was proposed schematically on the basis of the experimental results obtained.
Studies of the Organic Reactions of Metal Carbonyls. XV.The Reaction of Potassium Iron Carbonylates with Various Kinds of Olefin Oxides
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Mitsudo Takeaki , Masada Hiromitsu 
Published: July 2006

Abstract
The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4 and K2Fe2-(CO)8) and different olefin oxides has been studied. 1,2-Olefin oxides generally react with these carbonylates and carbon monoxide under an atmospheric pressure and at 30°C. This reduction gives the corresponding terminal olefins and the internal olefins which are formed from the 1-olefins by isomerization. Internal olefin oxides do not react with the carbonylates under the reaction conditions employed. The reduction reaction seems to compete with the carbonylation reaction. A mechanism for the reduction reaction is suggested.
A Study of Valence Tautomerism of Cycloheptatriene-Norcaradiene
Authors: Tsuji Teruji , Teratake Shuji , Tanida Hiroshi 
Published: July 2006

Abstract
Rates of the Diels-Alder reaction of cycloheptatriene, tricyclo[4.3.1.0]deca-2,4-diene, 1,3-cyclohexadiene, and cis-bicyclo[4.3.0]nona-2,4-diene with excess of fumaryl chloride were measured using a dilatometer. Comparison of the rate of cycloheptatriene with that of other olefins raises the question of the free energy difference so far estimated between cycloheptatriene and norcaradiene, which has been proposed to exist in equilibrium. It is suggested that the most preferable mechanism of the Diels-Alder reaction of cycloheptatriene is not through the norcaradiene isomer, but through the transition state of the norcaradiene structure.
Optical Spectra of Transition Metals in Na2O-P2O5 Glasses
Authors: Maekawa Takashi , Yokokawa Toshio , Niwa Kichizo 
Published: July 2006

Abstract
The optical spectra and the magnetic susceptibilities were obtained in sodium phosphate glasses containing transition metal ions. It was shown that the content of the transition metal ions of higher valency states increases with an increase in that of Na2O whenever an oxidation equilibrium occurs between two or more valency states. By combining the visible spectra analyzed from the viewpoint of the ligand field theory with the results of the magnetic susceptibility measurement, it was shown that most transition metals coordinate six oxygen atoms in the phosphates.
The Cyclization of Benzoylacetonitrile and Ketones by Ammonium Acetate
Authors: Sakurai Akio , Midorikawa Hiroshi 
Published: July 2006

Abstract
Several heterocyclic compounds, such as dihydropyridine, pyridine, tetrahydroquinoline and hexahydroquinoline derivatives, were prepared by the reaction of benzoylacetonitrile with such ketones as acetone, cyclopentanone, cyclohexanone, alkylcyclohexanone, alkylidenecyclohexanone, and aromatic α,β-unsaturated ketone in the presence of ammonium acetate.
Photochemical Analysis. I. Photonometric Titration of Thallic Ion by Uranyl Photoreduction Reaction
Authors: Yokoyama Yu , Ikeda Shigero 
Published: July 2006

Abstract
Photonometric titration of thallic ion is described, in which uranous ion, the titrant, is generated by photoreduction of uranyl ion in a sulfuric acid solution containing sodium lactate. Uranyl ion could be reduced with the light at wavelengths longer than 300 mμ, whereas thallic ion could not be reduced with the light in this wavelength range. Selective photoreduction of uranyl ion was accomplished by eliminating wavelengths below 300 mμ with a filter. In this photonometric titration, reaction solutions were irradiated without stirring at 29.5±0.5°C. The absorbance of uranous ion produced was measured at 655 mμ, every fixed irradiation time, and the absorbance was plotted against the irradiation time. Induction period, which means the period during which the absorbance remains actually zero, was in a linear relation with thallic concentration. Thus the titration of thallic ion was satisfactorily carried out in the concentration range from 0.01 to 0.1 mm. The results proved the feasibility of titration in a completely sealed container and suggest a possibility of titration on a microvolume of reaction solution.
Electronic Absorption Spectra of the Alkali Metal Complexes with Bipyridine
Authors: Torii Yasuo , Yazaki Takanori , Kaizu Youkoh , Murasato Shigetaka , Kobayashi Hiroshi 
Published: July 2006

Abstract
Electronic absorption spectra of the alkali metal complexes with 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine or 5,5′-dimethyl-2,2′-bipyridine have been observed in tetrahydrofuran solutions. Each spectrum has four major bands in the near infrared, visible and near ultraviolet regions, and is essentially due to the π–π*transitions in the negative ion (extra π electron trapping state) of bipyridine or its dimethyl derivatives coordinating to a metal ion. The band about 18000 cm−1 is the most sensitive to the metal ion species involved and assigned to a transition with the polarization parallel to the short axis of the bipyridine molecule. Each absorption band of the bipyrdine negative ion shows characteristic spectral shift upon CH3-substitutions in its peripheral positions. This CH3-substitution effect on the absorption spectra of bipyridine negative ion is quite different from that of complexes including neutral bipyridines and gives a basis of the criterion to determine whether the coordinating bipyridine in a certain bipyridine complex do exist in negative ion (π electron trapping state) or not.
Evaluation of the Activation Energies of Radical Substitution Reactions in the Gaseous Phase. II. An Approximate Formula with Two Constants
Authors: Kagiya Tsutomu , Sumida Yūzō , Inoue Tokuji 
Published: July 2006

Abstract
The following approximate formula for evaluating the activation energies of radical substitution reactions has been derived from the formula proposed in a previous paper:
Ea=Di−εDf(1+δDi)
where Di and Df are the bond dissociation energies of the initial and the final bonds. The calculated values are in good accordance with the observed values within ±2.0 kcal/mol. The empirical formulae, proposed by Evans-Polanyi and Semenov et al., between the activation energy and the reaction heat have been derived from this approximate formula. The Hammett-type rule has also been observed to hold in radical substitution reactions, and the substituent constants and the reaction constants have been determined by the use of the formula. A good correlation between the bond dissociation energy of the initial molecule and the radical reactivity index, delocalizability, based on the quantum chemical standpoint, has also been observed.
The Size and Shape of the Component Molecules as the Factors Determining the Electronic Structure of Crystal Complexes
Authors: Matsunaga Yoshio 
Published: July 2006

Abstract
The molecular complexes of six aromatic diamines with various acceptors were classified into those complexes having essentially non-bonding ground states and those having dative ground states on the basis of their vibrational spectra. A method to arrange the complexes by the difference between the ionization potential of the donor molecule and the electron affinity of the acceptor molecule was proposed to demonstrate how important the size and shape of the component molecules are as the factors determining the electronic structures of crystal complexes. The electrostatic energies per molecule in 1 : 1 crystal complexes were found to range from 2.3 to 2.6 eV.
The Chemistry of Protactinium. VIII. Synergistic Effect of Di-isobutyl Carbinol on the Pa(V)-TTA-Benzene Solvent Extraction System
Authors: Suzuki Shin , Inoue Yasushi 
Published: July 2006

Abstract
For the purpose of understanding the behavior of protactinium in a perchloric acid solution toward TTA-benzene extraction, the effect of di-isobutyl carbinol (DIBC) on the extraction was studied. A marked synergism was observed. As a result of a detailed investigation of such things as the effects of the TTA concentration, of the DIBC concentration, and of the acidity, the unified mechanism of TTA-benzene and TTA-DIBC-benzene extraction is considered to be a series of successive reactions, (1) through (4), with an increase in the DIBC concentration:
PaOm(OH)n5−2m−n+4HT=Pa(OH)2T3(HT)+(m+n−2)H2O+(5−2m−n)H+
Pa(OH)2T3(HT)→PaOT3(HT) (slow, irreversible) (1)
PaOm(OH)n5−2m−n+4HT=Pa(OH)2T3(HT)B+(m+n−2)H2O+(5−2m−n)H+
Pa(OH)2T3(HT)B→PaOT3(HT)B (slow, irreversible) (2)
PaOm(OH)n2−2m−n+3HT+B=Pa(OH)2T3B+(m+n−2)H2O+(5−2m−n)H+
Pa(OH)2T3B→PaOT3B (slow, irreversible) (3)
PaOm(OH)n5−2m−n+3HT+2B=Pa(OH)2T3B2+(m+n−2)H2O+(5−2m−n)H+
Pa(OH)2T3B2→PaOT3B2 (slow, irreversible) (4)
The slow, irreversible reaction in each step indicates the irreversible formation of unstrippable species in the organic phase with aging. The absorption spectral measurements gave results consistent with this conclusion.
The Viscosities of Aqueous Solutions Containing Metal Complexes. II. trans-1,2-Cy clohexanediaminetetraacetato Complexes
Authors: Yasuda Motoo 
Published: July 2006

Abstract
The viscosities of aqueous solutions containing metal chelate formed with trans-1,2-cyclohexanediaminetetraacetic acid (H4cydta) were measured with a Cannon-Fenske capillary viscometer. Measurements were made in a Shibata viscosity bath maintained at 25±0.01°C. The Jones-Dole viscosity B-coefficient of the cydta4− chelates is larger than that of the corresponding ethylenediaminetetraacetato (edta4−) chelates, as may be expected. The B-value of the Co (III) chelate [Co cydta]− is much smaller than that of any of the divalent metal cydta4− chelates studied. This fact, the same as in the case of the edta4− chelates, may indicate that the Co (III) chelate has a marked stable hexa-coordinated structure, while divalent metal chelates do not have such a stable hexa-coordinated structure as the Co (III) chelate.
Dioxouraniun(VI) Complexes of Schiff Bases Obtained from Substituted Salicylaldehydes and Alkyl Amines
Authors: Yamada Shoichiro , Takeuchi Akira 
Published: July 2006

Abstract
Dioxouranium(VI) complexes have been examined with Schiff bases obtained from substituted salicylaldehydes and alkyl amines. Many new complexes of the type abbreviated as UO2−(NO3)2(X-SAL·R·H)2 have been prepared as orange-red crystals. The notation X denotes H, 5,6-benzo and 3-CH3O, and R represents alkyl groups. Infrared spectra indicate that there is no uncoordinated nitrate ion, and that the nitrate ions are coordinated with the uranium(VI) ion as unidentate ligands in these complexes. It is to be noted that the molecules, and not anions, of the Schiff bases are coordinated with the metal ions, as in many other dioxouranium(VI) complexes.
The Excited States of Acridine Dyes. I. An ESR Study of the Triplet State
Authors: Kubota Yukio , Miura Masaji 
Published: July 2006

Abstract
The lowest triplet state of acridine dyes has been studied by an ESR technique over a wide range of concentration and in various solvents. The ESR spectra of the triplet state have been observed at a resonance field of ca. 1550 gauss, corresponding to the ΔM=2 transitions. The ESR data characteristic of the triplet state depend on the dye concentration; this has been interpreted as being due to the association of dye molecules. The values of the zero-field splitting parameter, D*, calculated from the ΔM=2 transition spectra lead to the assignment of the lowest triplet state of acridine dyes as the (π−π*) state.
Non-Newtonian Flow of Water-in-Oil Emulsions
Authors: Suzuki Kazushige , Matsumoto Sachio , Watanabe Takehiko , Ono Sôzaburo 
Published: July 2006

Abstract
In order to obtain information on the dispersion state of W/O type emulsions, the steady-flow viscosity in a wide shear range has been studied using a capillary type viscometer. Emulsions prepared by using Arlacel 83 or Arlacel 60, are classified according to the kind of hydrocarbon used as the suspending fluid, i.e., benzene, cyclohexane, liquid paraffin, isopropyl myristate, and squalane systems, respectively. Although all systems show the so-called shear thinning flow, shear dependence of the viscosity is not only influenced by the disperse phase concentration and emulsifier concentration, but is also much effected by the kind of suspending fluid. Such non-Newtonian behavior is observed markedly in benzene systems. It may thus be assumed that the water droplets in benzene have a tendency to form a large aggregate not easily redispersed under shear. The formation of aggregate may be facilitated by the disturbance of the orientation of the adsorbed emulsifier molecules at the interface due to the mutual interaction between the π-electron in benzene molecule and the emulsifier molecule.
The Molecular and Crystal Structure of trans-Dinitrotetramminecobalt(III) Nitrate Monohydrate
Authors: Oonishi Isao , Muto Fumio , Komiyama Yoshimichi 
Published: July 2006

Abstract
The crystal structure of trans-dinitrotetramminecobalt(III) nitrate monohydrate [Co(NO2)2-(NH3)4]NO3·H2O has been determined from three dimensional X-ray diffraction data. The dimensions of orthorhombic unit cell are: a=10.02 Å, b=6.02 Å, c=16.84 Å, and Z=4. The space group is P212121. The structure has been refined by the three dimensional Fourier and least-squares method to R=0.103. The complex ion has a slightly distorted octahedral coordination with six N atoms at about 1.98 Å (two are N atoms of nitro groups and the others ammonium groups). The complexes are tightly bound together by N–H···O and O–H···O interactions, constructing a three dimensional network.
ESR Studies of the Negative Ions of Biphenyl Derivatives. III. Restricted Rotation of Alkyl Group in Some ortho or para Higher Alkylated Biphenyl Anion Radicals
Authors: Ishizu Kazuhiko , Mukai Kazuo , Hasegawa Hideo , Kubo Koichi , Nishiguchi Hiroaki , Deguchi Yasuo 
Published: July 2006

Abstract
The electron spin resonance has been observed for the anion radicals of 4,4′-diethyl biphenyl, 4,4′-diisopropyl biphenyl, 4,4′-dicyclohexyl biphenyl, 2,2′-diethyl biphenyl, and 2,2′-diiso-propyl biphenyl. Both of the β- and γ-proton coupling constants of alkyl groups have been precisely determined, and the positive temperature dependence has been verified for the β-proton coupling constant of 4,4′-dialkyl biphenyls. The ratio (R) of β-proton coupling constant of the other alkyls to the methyl proton coupling constant has been derived, and the evidence of the restricted rotation has been widely established for each derivative based on the angular dependence of the β-proton coupling constant, which can be expressed as follows:
ai β=ρπ&lt;Q&gt;, Q=B0+Bcos2θ
The minimum R value obtained for 2,2′-diethyl biphenyl enabled us to assume that a rotation of the alkyl group would be tightly locked at the ortho position. The R value of 2,2′-diisopropyl biphenyl revealed that the isopropyl β-proton would lie on the biphenyl aromatic plane. The anomalous R values associated with the ortho-alkylated biphenyls can be well understood as resulting from the facts that anion radicals have a more dominant character than do neutral molecules to reduce a twisting angle between the two phenyls, and that the free rotation of the alkyl group is strongly restrained by the steric hindrance between the alkyl group and the closely-oriented ortho-ring proton.
The Kinetics of the Ligand-substitution Reactions of Nitrilotriacetatoniccolate(II) Complexes with trans-1,2-Cyclohexanediaminetetraacetate Ions
Authors: Kimura Masaru 
Published: July 2006

Abstract
The kinetics of the ligand-substitution reactions of the nitrilotriacetatoniccolate(II) complexes with trans-1,2-cyclohexanediaminetetraacetate (CyDTA) ions were studied polarographically from pH 4.8 to 5.8 at an ionic strength of 0.2 and at 25°C. The reactions were found to proceed only through the dissociation reactions of the nitrilotriacetatoniccolate(II) complexes. The rate constants of the dissociation reactions were also determined. In contrast to the reactions of the same complex with ethylenediaminetetraacetate (EDTA) ions and N-2-hydroxyethylene-diaminetriacetate (HEDTA) ions, there were no direct reactions of the nitrilotriacetatoniccolate-(II) complexes with CyDTA ions. The reaction was of the first order in respect to the concentration of the nickel-complex and independent of the CyDTA concentration; the reaction of the complex with CyDTA ions was found to have the different mechanisms from the similar reaction with EDTA and HEDTA, and to be due to the steric effect of the cyclohexane ring in the CyDTA molecule.
Spectroscopic Studies of the Mixture of Dialkylaluminum 2-Aminoethoxide (AlR2OCH2CH2NR′2)2 and Trialkylaluminum (AlR″3)2
Authors: Sato Hideo , Tarao Ryokichi , Higashi Hiromi 
Published: July 2006

Abstract
The proton magnetic resonance and infrared spectra of the mixtures of dialkylaluminum 2-aminoethoxide (AlR2OCH2CH2NR′2)2 and trialkylaluminum (AlR″3)2 were measured. Special attention was paid to the infrared frequencies of the NH2 stretching and scissors bands and to the chemical shifts of the methyl groups attached to the aluminum and nitrogen atoms. From the results it was concluded that (AlR″3)2 reacts with (AlR2OCH2CH2NR′2)2 to form a 1:1 coordination compound AlR2OCH2CH2NR′2→AlR″3 quantitatively. At the same time, the redistribution and exchange reactions of the alkyl groups were observed.
Configuration and Conformation of So-called Bis(alkylidenearylamines)
Authors: Funabashi Masuo , Iwakawa Masaharu , Yoshimura Juji 
Published: July 2006

Abstract
The proposed structures of the dimeric products obtained from aliphatic aldehydes and arylamines were reexamined by IR and NMR spectra. The 1,2,3,4-tetrahydroquinoline structure was ascertained in the case of acetaldehyde or propionaldehyde, and aldolic structure was confirmed in the case of n-butyraldehyde. It was observed that the latter readily isomerizes to the former type in the presence of acetic acid. Conformational analysis of a racemic pair of the former (IIIa–c: 2,4-disubstituted, IIId- 2,3,4-trisubstituted) indicated that two isomers of IIIa–c (one has 2-equatorial, 4-quasi-equatorial and the other 2-equatorial, 4-quasi-axial substituents) have a flattened half-chair conformation and two isomers of Hid (one has 2,3-diequatorial, 4-quasi-equatorial, and the other 2-equatorial, 3-axial, 4-quasi-axial substituents) have a more remarkably flattened half-chair, i. e. a nearly plane structure. The acylation of ring nitrogen enhanced this tendency, and one of the 1-acetyl derivatives of III was deduced to have a twist half-boat conformation.
Studies on s-Triazines. II. Cotrimerization of Trichloroacetonitrile with Thiocyanates
Authors: Wakabayashi Ko , Tsunoda Masaru , Suzuki Yasushi 
Published: July 2006

Abstract
2-Substituted thio-4,6-bis(trichloromethyl)-s-triazmes, a new class of s-triazine derivatives, were obtained by the cotrimerization of CCl3CN with a wide variety of thiocyanates. Generally, the reaction proceeded smoothly at ordinary pressure in the presence of hydrogen chloride or the combined catalyst, Friedel-Crafts catalyst-hydrogen chloride.
Conformation and S=O Stretching Absorptions of Simple Sulfoxides
Authors: Oki Michinori , Oka Isao , Sakaguchi Katsushiro 
Published: July 2006

Abstract
The infrared S=O stretching absorptions of several simple sulfoxides have been measured. Some sulfoxides show one absorption maximum, whereas others show two. These results may be attributed to the rotational isomerism about the S–C axis. Convincing evidence for this conclusion has been obtained by the measurement of the spectra of methyl isopropyl sulfoxide at various temperatures.