bluuebunny/crossref_metadata_2025 huggingface dataset:
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

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>Br>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>H>Cl>Ac. This order in the ferrocene series was opposite to that in the p-substituted bromobenzene series: CN>Ac>Br>H>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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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, 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

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

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

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

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

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.
Asymmetric Reactions. III. Stereoselectivity Difference between Grignard and Alkyllithium Reactions with 2,3-O-Substituted-d-glyceraldehydes
Authors: Ohgo Yoshiaki , Yoshimura Juji , Kono Masami , Sato Tetsuo
Published: July 2006

Stereoselectivity has been investigated in addition reactions of 2,3-O-isopropylidene-d-glyceraldehyde (I) or 2,3-di-O-benzyl-d-glyceraldehyde (II) with phenylmagnesium bromide or phenyllithium. Stereoselectivity difference between the Grignard and phenyllithium reactions occurred in the case of compound (I): the phenyllithium reaction gives threo and the Grignard reaction erythro products predominantly. On the other hand, no difference in stereoselectivity has been observed between the reactions with 2,3-di-O-benzyl-d-glyceraldehyde (II): both reactions gave threo product predominantly.
Kinetics and Mechanism of the Oxidation of Citric and Glyoxylic Acids by Cerium (IV) Ion
Authors: Sengupta Kalyan K
Published: July 2006

The mechanism proposed by Waters (J. Chem. Soc., 1955, 217) for the oxidation of α-hydroxy acids by manganic pyrophosphate accounts for the kinetics of oxidation of citric acid by cerium(IV) ion. The oxidation appears to proceed through the initial formation of complex and subsequently through free radicals.
Kinetics of Reactions of Amines with Alkene Oxides
Authors: Sundaram P K , Sharma M M
Published: July 2006

A variety of amines such as piperazine, pyrrolidine, morpholine, dialkyl amines, alkanolamines etc. were reacted with ethylene-, propylene-, and 1,2-butylene oxides in aqueous medium. Most of the experiments were made at 20°C. For some typical amines kinetic runs were made over a wide temperature range to obtain values of activation energy. Theoretical aspects of the reaction are discussed. It is shown that the method suggested by Swain and Scott could be used to correlate the rate constants. A close relationship exists between the relative rates of reaction of amines with CO2, COS, CS2 and alkene oxides.
Copper(II) Complexes of Ethylenediaminemonoacetic Acid (EDMA). A Polarographic Study of the Solution Equilibria between the Copper(II) Ion and EDMA and the Preparation of Copper(II)-EDMA Complexes
Authors: Fujii Yuki , Kodama Mutsuo
Published: July 2006

In the present paper, the solution equilibria between the copper(II) ion and ethylenediaminemonoacetic acid (EDMA) were determined polarographically and, then copper(II)-EDMA complexes were prepared and characterized using ion-exchange chromatography and the visible and infrared absorption spectra. Since copper(II) ions in an EDMA solution behave reversibly in a polarographic electrolysis, the composition and the stability constants of copper(II)-EDMA complexes were determined from the dependence of the half-wave potential on the concentration of uncomplexed EDMA by employing a modification of the Deford-Hume method. The copper (II) ion was found to form complexes of 1-to-1 and 1-to-2 compositions with EDMA. Their successive formation constants, K1 and K2, were 2.52×1013 and 1.10×108 respectively. The copper(II)-EDMA complex with a 1-to-1 composition was easily isolated from an aqueous solution of pH 3.0–4.0. On the other hand, the complex with a 1-to-2 composition could be isolated in a low yield by adding ethanol from a solution containing an excess amount of EDMA in the pH range from 10.0 to 11.0. From the infrared spectra and the ion-exchange chromatographic behavior, the ethylenediaminemonoacetate ion in the complexes was concluded to function as a tridentate ligand.
The Ion Exchange of a Mixture of Er and Tm with HEDTA
Authors: Hagiwara Zenzi , Oki Hideo
Published: July 2006

Under experimental conditions similar to those in the elution system of the rare earth with a dilute HEDTA eluant, the Er-Tm separation factor has been found in the system of HEDTA and Dowex 50W, X-8, 50–100 mesh. The values for this pair, 1.57 at 25°C and 1.63 at 60°C were in agreement with the values calculated from the stability constants of the rare earth-HEDTA chelates. Further, an equimolar mixture of Er and Tm has been eluted with a 0.015m HEDTA solution buffered with ammonium hydroxide. Under the present experimental conditions, the adsorption band of each rare earth reached a steady state after it had moved down through the hydrogen-retaining bed to a distance several times the initial band length. Several series of experimental data were used for analyses of the adsorption band from the point of view of rate theory. It was concluded that the present ion-exchange process with a HEDTA eluant was controlled by film diffusion as the rate-determining step. The plate-height values were also found to be functions of the flow rate.
The Reaction of Carbon Suboxide with Alicyclic Diketones and with Phenols. Formation and Structure of Pyrone Derivatives
Authors: Omori Akira , Sonoda Noboru , Uchida Yuzo , Tsutsumi Shigeru
Published: July 2006

The reactions of carbon suboxide with alicyclic diketones and with phenols were found to give various pyrone derivatives. From the reaction of 5,5-dimethyl-1,3-cyclohexanedione, 4-hydroxy-7,7-dimethyl-5,6,7,8-tetrahydro-2H-benzo[b]pyran-2,5-dione (II) was produced in the presence of a sulfuric acid catalyst. However, the reaction with 1,2-cyclohexanedione gave the malonic acid diester (III), and the formation of corresponding pyrone was not observed. The reaction of phenols with carbon suboxide gave only esters of malonic acid in the presence of the sulfuric acid catalyst, whereas cyclization to coumarin derivatives occurred on the presence of aluminum trichloride, in addition to the formation of the esters. The structure of the pyrone derivatives and the possible reaction mechanism were discussed.
Sugars Containing a Carbon-phosphorus Bond. I. Photochemical Addition of Diethyl Thiophosphonate to Unsaturated Sugars
Authors: Kumamoto Kazuo , Yoshida Hiroshi , Ogata Tsuyoshi , Inokawa Saburo
Published: July 2006

Sugars containing a carbon-phosphorus bond were synthesized by the photochemical addition of diethyl thiophosphonate to unsaturated sugars. By UV illumination from a high-pressure mercury lamp in the presence of diethyl thiophosphonate, -d-glucal gave 1,5-anhydro-2-deoxy-2-(diethyl thiophosphonate)-d-glucit; 3-deoxy-1,2;5,6-di-O-isopropylidene-α-d-erythro-hex-3-enose gave 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-d-glucofuranose and 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-d-galactofuranose (4:1 mol ratio); 6-O-benzyl-5-deoxy-1,2-O-isopropylidene-α-d-xylo-hexofuran-5-enose gave 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-d-glucofuranose and 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-l-idofuranose (2:5 or 5:2 mol ratio), and 5-deoxy-l,2-O-isopropylidene-3-O-methyl-α-d-xylofuranose-4-ene gave 5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-3-O-methyl-α-d-xylofuranose.
Nitroalkenylferrocene. III. Condensation Reaction of Acetylferrocene Using Lewis Acid and Cyclic Amine
Authors: Kono Hiromichi , Shiga Mikio , Motyoama Izumi , Hata Kazuo
Published: July 2006

Acetylferrocene reacted with nitromethane and morpholine in the presence of titanium(IV) chloride to give a Mannich base, 2-ferrocenyl-2-morpholino-1-nitropropane (7), whose sodium salt (8) was then converted to 2-ferrocenyl-1-nitropropene (9) by acidifying it with hydrochloric acid. In the presence of aluminum chloride in place of titanium (IV) chloride, acetylferrocene as well as 1,1′-diacetylferrocene dimerized to form α,β-unsaturated ketone, (10) or (11).
Kinetic Studies of Solvolysis. XVI. Phenolysis of cis- and trans-4-t-Butylcyclohexy p-Toluenesulfonates. Rates and Product Distribution
Authors: Okamoto Kunio , Saitô Seiki , Shingu Haruo
Published: July 2006

The rates of the phenolysis of cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates have been measured in the presence of equimolar amounts of triethylamine in phenol, phenol-benzene (3 : 1 by wt), and phenol-benzene (1 : 1 by wt) solvents. At 75°C, the axial isomer, i.e., the cis tosylate, phenolyzes more rapidly in the phenol-benzene mixture (1 : 1 by wt) than the equatorial isomer, i.e., the trans tosylate, by a factor of 3.08; this factor is not far from the axial-equatorial rate ratios observed in other hydroxylic solvents, indicating that phenol is a typical solvolytic solvent. Under the same reaction conditions as the rate measurements, the equatorial tosylate yields t-butylcyclo-hexene (72.5%), t-butylcyclohexyl phenyl ether (9.4%), predominantly inverted (cis-4-t-butylcyclo-hexyl) phenyl ether, and t-butylcyclohexylphenol (4.4%), whereas the axial tosylate yields t-butyl-cyclohexene (87%) and the phenyl ether (8.7%), largely inverted (trans-4-t-butylcyclohexyl) phenyl ether, but containing increasing amounts of retained (cis-4-t-butylcyclohexyl) and and rearranged (trans-3-t-butylcyclohexyl) ethers; the rest is a mixture of t-butylcyclohexylphenols (1.6%). The composition percentages of the retained phenyl ether obtained from the two tosylates, i.e., 20.4% for the cis tosylate and 12.9% for the trans tosylate, indicate the highest extents of retention for phenol among those known for any other hydroxylic solvents. The initially added t-butylcyclohexenes exert no influence on the olefin or on the phenyl ether composition, whereas triethylammonium and diethylammonium p-toluenesulfonates, when added initially, enhance the phenolysis rate and exert a small but definite influence on the composition of the phenyl ether. The hypothesis of the hydrogen-bridged cation, proposed in order to explain the enhanced rate of the cis isomer and in order to elucidate the retained solvolysis product, has been questioned by a consideration of the mechanism on the basis of the results of this phenolysis.
Reaction of Modified Polypropylene Fiber Containing the Glycidyl Group with Several Amines and Ammonia
Authors: Mizutani Yukio , Kusumoto K\={o}shi , Matsuoka Seishir\={o} , Tani Mitsuo , Suda Yoshio , Shirota Tadashi
Published: July 2006

Polypropylene was modified by the blending of the fine powdery copolymer of glycidyl methacrylate and divinyl benzene, and this modified polypropylene fiber was treated with diethyl amine, diethanol amine, monoethanol amine, and ammonia. The reactivity order was as follows: monoethanol amine>diethyl amine>diethanol amine= ammonia. Consequently, the resultant fiber showed water-wettability and could be dyed with an acidic dye.
Spectroscopic Investigation of Foreign Gas Effects upon CO2 Laser Frequencies
Authors: Suzuki Isao , Suzuki Shigeko
Published: July 2006

The change in the oscillation frequencies of a CO2 laser was examined when foreign gases were introduced into a cell placed inside the cavity. Several gases which have absorption bands around 10 μ region were investigated: sulfur hexafluoride, ammonia, ethylene, trans-dichloroethylene, methyl bromide, trichloroethylene, acrolein, and isopropyl alcohol. The CW laser oscillations in the P-branch of the 9.6 μ band as well as those in the R-branch of the 10.6 μ band were observed when some foreign gases with appropriate pressures were introduced in the cavity. It was also found that the presence of ammonia or methyl bromide even in a very low pressure suppressed the usually strong P(20) line of the 10.6 μ band. This is interpreted as due to a near coincidence of the laser line with one of the vibration-rotation transitions in these molecules.
Studies of the Mixed Chromium(III) Complexes Containing Ethylenediamine-N,N′-diacetic Acid
Authors: Fujii Yuki , Yamamoto Katsumi
Published: July 2006

Three new mixed chromium (III) complexes containing ethylenediamine-N,N′-diacetic acid (EDDA) and amino acid, [Cr(edda)(L)] (L= anion of glycine, α-alanine and β-alanine), were prepared from [Cr2(OH)2(edda)2]·6H2O. On the basis of their chemical analyses and the visible and infrared absorption spectra, the geometrical structure of the three mixed ligand complexes was estimated to be the facial form with respect to the coordinated three nitrogen atoms, where the configuration of the coordinated edda was inferred to take the β-form (cis with respect to the coordinated oxygen atoms of edda). The new mixed ligand complex containing the glycine anion, [Cr(ox)(gly)(en)]·H2O, was also prepared from cis-[Cr(ox)(H2O)2(en)]Br, and its geometry was discussed in the connection with its visible absorption spectrum.
Adsorption of N′-(2-Hydroxyethyl)-ethylenediamine-N,N,N′-triacetic Acid on the Hydrogen Form of Resin
Authors: Hagiwara Zenzi , Oki Hideo
Published: July 2006

The adsorption of HEDTA (H3Ch) on the hydrogen form of Dowex 50W, X-8, 100–200 mesh, has been studied as a function of the concentration of H3Ch in the aqueous phase. The experiments were performed by means of either the column or a combination of the column and batch methods, with the latter being employed for the adsorption of HEDTA on the resin in equilibrium with dilute solutions. In solutions up to approximately 0.07 mol/l, such as H3Ch, the experimental data are consistent with the Langmuir equation expressed by: [H3Ch]/(‾ChT⁄E)=1⁄Bk+[H3Ch]⁄B. The adsorbed amount is represented in the term ‾ChT⁄E, where ‾ChT is the total amount of cationic species of HEDTA on the resin, and E, the exchange capacity of resin. A good straight line is obtained with B=0.571 and K=0.420. The results show that, because of a high concentration of hydrogen ion inside the resin, the adsorbed HEDTA is present mainly in the H5Ch2+ species and partly in the H4Ch+ species.
Constitution of Mucilage from Ulva Conglobata. I. Separation of Rhamnobiose Derivative by Partial Methanolysis
Authors: Mita Kiyo
Published: July 2006

Partial methanolysis of the mucilage from Ulva conglobata gave methyl α-l-rhamnoside (29.07%), methyl α-d-xyloside (7.04%) and methyl α-d-glucoside (5.13%). Separation of a new disaccharide (methyl α-l-rhamnobioside, 3.4%) from methanolysate was achieved chromatographically. The biose was attacked by maltase but not by emulsin. The results and infrared spectrum show that the rhamnobiose derivative consists of rhamnose units linked by α-link.
The Diels-Alder Reactions of Polychloro-2,4-cyclohexadienones
Authors: Somekawa Kenichi , Matsuo Taku , Kumamoto Sanetada
Published: July 2006

2,3,4,5,6,6-Hexachloro-, 2,3,4,6,6-pentachloro-, and 2,4,6,6-tetrachloro-2,4-cyclohexadienones were found to undergo Diels-Alder reactions when the compounds were heated with such dienophiles as acrylic acid, methyl acrylate, methyl vinyl ketone, acrylonitrile, and ethyl vinyl ether. It was concluded, chiefly through analysis of these NMR spectra, that the reactions proceed stereospecifically to give a series of 7-substituted and polychlorinated bicyclo-[2.2.2] oct-5-en-2-ones, which is in agreement with the endo rule. The stereospecificity of these adducts does not, however, agree with the results of calculations by means of the perturbation method.
n–π* Electronic Spectra of 2-Methyl-1,4-naphthoquinone in the Vapour Phase
Authors: Baruah G D , Singh S Nath , Singh R S
Published: July 2006

The visible emission glow of 2-methyl 1,4-naphthoquinone has been excited by an uncondensed transformer discharge in the presence of flowing vapour of benzene. The vapour absorption spectrum of the molecule has also been investigated in the region 4900–3800 Å at different temperature.
The Yields of Photonuclear Reactions in Titanium and Vanadium with Bremsstrahlung up to 60 MeV
Authors: Oka Yoshinaga , Kato Toyoaki , Sato Nobuyoshi
Published: July 2006

The yields of a number of radioactive nuclei produced by (γ,xnyp) reactions on titanium and vanadium targets have been determined at four different bremsstrahlung maximum energies, 30, 45, 55 and 60 MeV, with the aid of radiochemical methods and gamma-ray spectrometric measurements. The linear electron accelerator of Tohoku University was the bremsstrahlung source. Yields have been expressed as production rates of given radioactive end-products relative to that of the 12C(γ,n)11C process. Over the range of energies investigated, the yield of each nuclide increases with increasing maximum energy. The yield of a reaction with the emission of more than one nucleon appeared to be strongly energy dependent. Reaction paths leading to the formation of each nuclide were investigated. The photoproduction of 47Ca from titanium has been observed.
Studies of Aminosugars. XXII. The Total Synthesis of Kanamycin A
Authors: Umezawa Sumio , Tatsuta Kuniaki , Koto Shinkiti
Published: July 2006

6-O-(3-Amino-3-deoxy-α-d-glucopyranosyl)-2-deoxystreptamine, which was previously synthesized, was masked with carbobenzoxy, isopropylidene and benzyl groups to give 6-O-(2-O-benzyl-3-carbobenzoxyamino-3-deoxy-4,6-O-isopropylidene-α-d-glucopyranosyl)-N,N′-dicarbobenzoxy-2-deoxystreptamine, with which 2,3,4-tri-O-benzyl-6-(N-benzylacetamido)-6-deoxy-α-d-glucopyranosyl chloride was condensed by a modified Koenigs-Knorr reaction, to give an α,α-diglycoside compound. The identity of the product with a substance of the same structure derived from natural kanamycin A was shown. Removal of the masking groups gave the synthetic kanamycin A, which was identical to the natural specimen.
Kinetics and Mechanism of Oxidation of d-Glucose and d-Fructose by Potassium Ferricyanide in the Presence of Ammonia
Authors: Gupta K C , Singh M P
Published: July 2006

The reaction rate is independent of the concentration of ferricyanide ion and directly proportional to both the reducing sugar and ammonia concentration. The reaction is of general basic catalysis in nature. The reaction rate is decreased with the addition of ammonium chloride due to common ion effect. The catalytic constants kOH− and kNH3 have been calculated graphically. The reaction rate is, also, decreased with the gradual decrease in dielectric constant of the solvent and increased with the gradual increase in ionic strength. The rate expression obtained is as:

(Remark: Graphics omitted.)
Copolymerization of β-Cyanoacrolein with Acrylonitrile
Authors: Takemura Ichiro , Sumitomo Hiroshi
Published: July 2006

Radical initiated copolymerization of β-cyanoacrolein (CAL, M2) with acrylonitrile (M1) in benzene at 60°C was investigated. The monomer reactivity ratios were determined to be r1=3.2 and r2=0. The copolymerization behavior is discussed in comparison with that in the system of styrene and CAL previously described. The Q and e values of CAL were also estimated to be 0.53 and 2.07, respectively, which were compared with those of other polar monomers.
Electrical Conductance of Molten Salt Systems: Ag2O-B2O3 and Ag2O-Na2O-B2O3
Authors: Kodama Hiroshi , Kimura Yoshihiro , Yokokawa Toshio , Niwa Kichizo
Published: July 2006

The electrical resistance of the Ag2O-B2O3 and Ag2O-Na2O-B2O3 systems has been measured in the approximate temperature range from 750 to 1000°C. The equivalent conductance at 900°C and the activation energy of the conductance for the Ag2O-B2O3 system were calculated. They were then compared with the corresponding values of alkali borate melts. The results led to the conclusion that the silver ion is not bound to the oxygen ion in the melt, but behaves like Li+, Na+, and K+ which are known to be monovalent network modifiers and to be free to move in the melt.
Amination of Benzoic Acid in the γ-Radiolysis of Liquid Ammonia
Authors: Sakumoto Akihisa
Published: July 2006

Ammonia and aqueous ammonia solutions of benzoic acid, 14C-carboxyl labeled, were irradiated with 60Co γ-rays at absorbed doses of 1.9×1020 and 4.4×1020eV/g respectively. The irradiation temperature was 0°C in both cases. An isotope dilution method was applied to measure the products in irradiated solutions. The G values of o-, m-, and p-aminobenzoic acids were 0.016, 0.022, and 0.027 respectively in an ammonia solution. On the other hand, the G values of products in an aqueous ammonia solution were 0.011, 0.013, and 0.017 for o-, m-, and p-aminobenzoic acids and 0.029, 0.033, and 0.040 for o-, m-, and p-hydroxybenzoic acids. The disappearance of benzoic acid in an ammonia solution corresponded to a G value of about 1.46. From the ratio of the relative partial rate factors, it was deduced that the aminating agent was the amino radical in both cases.
Reaction of trans-Stilbene with n-Butyllithium in Tetrahydrofuran
Authors: Okamoto Yoshio , Kato Masahiko , Yuki Heimei
Published: July 2006

The reaction of trans-stilbene with n-butyllithium was investigated in tetrahydrofuran at 0°C. The structures of the products fractionated by column chromatography were determined by elementary analysis, a molecular-weight determination, and a study of the IR, UV, and NMR spectra. The main products were 1,2-diphenylhexane, 1,2-diphenylethane, and 1,2,3-triphenyl-propene which was formed by the cleavage of a C–C bond of a product. The reaction mixture showed an ESR signal. The observed results are explained in terms of the anionic copolymerization of trans-stilbene and styrene reported previously.
Semi-Empirical ASMO SCF Method for the Valence Electron System. The Electronic Structures of Protonated Pyridinium and Diazinium Cations
Authors: Kato Hiroshi , Katô Hajime , Konishi Hideyuki , Yonezawa Teijiro
Published: July 2006

Using a semi-empirical ASMO SCF method for valence electron systems previously proposed by the present authors, the valence shell electronic structures of various protonated azines are investigated. The compounds treated in the present paper are monoprotonated pyridinium, mono-, and diprotonated diazinium cations. The calculated results show that quite large charge redistributions on both σ and π electron systems in these cations take place in the protonation, while about a 0.7 e charge migrates to the attached protons. As to the transition energies, the lowest π–π* transitions exhibit slight red shifts, while the n–π* transitions would be expected to cause large blue shifts by means of protonation. Several models for protonated cations are compared, and the configuration where the proton is situated on the bisector of the CNC(N) angle and in the molecular plane is shown to be the most stable one. The changes in Fock’s operators upon protonation are also briefly discussed.
Some Thermal Properties of Metal Chelates of o-Acylphenols and of Their Ketimine Derivatives
Authors: Matsumoto Seiichiro , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

The beryllium chelates of 2-hydroxy-3-methylacetophenone, 2-hydroxy-3-isopropylisobutyrophenone and 2-hydroxyacetophenone, and the copper- and nickel chelates of the ketimine derivatives of 2-trifluoroacetylphenol and 2-hydroxyisobutyrophenone in addition to the above o-acylphenols were synthesized. The thermal stability and relative volatility of these chelate compounds, measured by means of a thermogravimetric method, were found to be strongly increased by introduction of bulky alkyl or trifluoromethyl groups.
Cobalt(IV) Ammine Complexes with 5-Nitrosalicylato or Similar Ligands. III. Electric Resistivity, Magnetic Susceptibility, and ESR
Authors: Yamamoto Yoshihisa
Published: July 2006

The electric and magnetic properties of a series of 5-nitrosalicyclato ammine cobalt (IV) complexes (paramagnetic), the salicylato ammine cobalt (III) complex (diamagnetic), μ-superoxodicobalt ammine complexes (paramagnetic), and the μ-peroxodicobalt ammine complex were studied. The resistivity(ρ) at room temperature and the energy gap(ε) for paramagnetic complexes were in the range of, ρ=7.6×1011−1.5×1010Ω cm and ε=0.75−1.1 eV, whereas those for diamagnetic complexes were in the range of ρ=1012−1014Ω cm and ε=0.75−1.2 eV. The magnetic susceptibilities of the paramagnetic complexes obeyed the Curie-Weiss law, with comparatively large Curie-Weiss constants (−18−26°). The g-values and line widths (ΔHmsl) in the ESR signals at room temperature were determined for powdered samples of 5-nitrosalicylatotetraamminecobalt(IV) complexes and their derivatives. The ESR parameters obtained were in the range of g=2.0030−2.0070 and ΔHmsl=22.0−30.6 Oe for powders.
Amylase Action in Maltodextrin-Sodium Dodecylsulfate Solution
Authors: Sakon Ken-ichi , Watanabe Takehiko , Ono Sôzaburo
Published: July 2006

Enzyme catalyzed hydrolysis of maltodextrin was studied with enzyme-maltodextrin and enzyme-maltodextrin-sodium dodecylsulfate systems. Sodium dodecylsulfate (SDS) is a complex forming agent for maltodextrin. When endo-enzyme such as Taka-amylase A was used as the enzyme, ratio of the initial velocity of the hydrolysis of the system containing SDS to that without SDS decreases with the increase of degree of polymerization (D.P.) of the maltodextrin and becomes zero with the maltodextrin of D.P. above about 60. When the liquefying α-amylase of Bacillus subtilis was used as an endo-enzyme, a similar result was also obtained. When exo-enzyme such as Glucoamylase of Rh. Delemar was used, the ratio decreases gradually with the increase of D.P. of maltodextrin, and remains in a relatively high level even in the case of maltodextrin of D.P. above 60. In the case of Taka-amylase A, the enzyme action is suppressed by the presence of the stiff helical segments of SDS complex and the initial velocity of the system with SDS decreases compared with the one without SDS. In the case of Glucoamylase, the presence of the stiff helical segment does not distinctively induce such a depression of the enzyme action as that in the case of Taka-amylase A. The depression is partly dependent on the inhibitory interaction of SDS with the enzyme.
A One-dimensional Model of a Conduction Calorimeter
Authors: Hattori Masaru , Tanaka Satohiro , Amaya Kazuo
Published: July 2006

An idealized one-dimensional model of a conduction calorimeter, composed of a container in which thermal change occurs, a thermal bath, and a solid thermal conductor connecting the container with the thermal bath, is presented. The boundary-value problem of heat conduction in the model calorimeter is solved by the Laplace transformation method. A proportionality relation between the quantity of heat evolved in the calorimeter container and the area enclosed by the recorded temperature curve and the time axis is establised.
The Density and Molar Volume of a Binary Liquid, B2O3-H2O
Authors: Kodama Hiroshi , Yokokawa Toshio , Niwa Kichizo
Published: July 2006

The density of the binary B2O3-H2O liquid system with concentrations of from 4.9 to 83.0 mol% B2O3 has been measured, and the mean volume expansivity has been calculated. The molar volume and the expansivity of this system has then been compared with those of other binary borates. The experimental results suggest a change in the boron-to-oxygen coordination number between the 3B2O3·H2O and B2O3·H2O compositions. The thermal expansivity of this system shows a different trend from those of alkali borate melts.