bluuebunny/crossref_metadata_2025 huggingface dataset:
Resolution of Amino Acids. VIII. The Preparation of the Four Optical Isomers of β-Hydroxyaspartic Acid
Authors: Okai Hideo , Imamura Naokazu , Izumiya Nobuo
Published: July 2006

The ammonolysis of cis-epoxy succinic acid yielded threo-hydroxy-Dl-aspartic acid exclusively, but that of trans-epoxy acid produced a mixture of 68% erythro- and 32% threo-hydroxyaspartic acid. This mixture was separated into the two pure diastereomers through either a Dowex 1 column chromatography or fractional crystallization after the mixture had been changed to ammonium salt. The threo- and erythro-Dl-amino acids so prepared were resolved by optically active lysine and ornithine respectively. The contribution (partial molar rotation) of the α-and β-asymmetric centers to the observed molar rotations of the optically active diastereomeric hydroxyaspartic acids in water and 5 n hydrochloric acid was calculated.
Effect of Pressure on Electrical and Optical Behaviour of Quaterrylene, C40H20
Authors: Shirotani Ichimin , Inokuchi Hiroo , Akimoto Shun-iti
Published: July 2006

The temperature dependence of the electrical resistance of the compressed quaterrylene was studied over the temperature range from 300°K to 1000°K under high pressure. The intrinsic energy gap and also the extrinsic energy gap, which is formed by oxygen adsorbed onto the organic crystals, decreased with an increase in the pressure. These changes were dependent linearly on the pressure. The pressure effect on the absorption spectra of the evaporated film and that on the spectra of the solid solution of quaterrylene were observed. It was found that the value of the peak-shift, 8–9×10−6 eV/bar, is comparable to the contraction of the thermal energy gap, 9×10−6 eV/bar, determined from the temperature dependence of the electrical resistance.
Studies of Metallic Hydrides. I. Synthesis of Stoichiometric Hydrides of Group IVb Metals
Authors: Oka Akira
Published: July 2006

Formerly, hydrides of transition metals were generally treated as solid solutions or as hydrogen-occluding systems. It has been said that the elements in the IVb group of the periodic table, whose hydrides are typically metallic, do not form any stable hydride with a stoichiometric composition. The author intends to report the establishment of a process of synthesizing these hydrides, by which process the conditions necessary for the stoichiometric synthesis of IVb metal hydrides were determined.
A New Method of Continuous Gas Chromatography
Authors: Hiratsuka Shigeo , Ichikawa Atsunobu
Published: July 2006

A method is proposed for the continuous analysis of multi-components mixture of volatile compounds by means of gas chromatograph. In the method, a sinusoidal concentration wave of sample gas mixture is introduced continuously into a column of gas chromatograph and the mole fraction of each component can be determined from the amplitude attenuation and the phase-shift measured at the points of several length along the column. The principle of the method is described and the conditions which have to be considered in selecting the column and the angular frequency are discussed. Experiments with two components, nitrogen and oxygen, gas mixture employing a Molecular Sieve 5A column and the hydrogen carrier gas indicate that the principle is valid and that the continuous analysis of multi-components mixture is successful.
Relation between Paper Chromatographic Rf-Values and Two Phase-Distribution Ratios of Phosphate Ions
Authors: Ohashi Shigeru , Hirai Yoshiaki , Waki Hirohiko
Published: July 2006

An easy and useful method reflecting the behaviors of phosphate ions in paper chromatography was proposed. Under some assumption, the correlations between Rf in the paper chromatography and the distribution ratio Ds or Df in the solvent extraction or in the filter paper batch equilibration were investigated. When the water-miscible solvents are used, Df-values may reflect Rf-values considerably well. If the water-immiscible solvents are used, rather Ds-values reflect Rf-values well. Although the partition only has so far been considered in these types of paper chromatography, the results showed that the adsorption phenomena cannot entirely be ignored in some solvent systems like a basic benzyl alcohol system.
The Optical Resolution and Circular Dichroism of trans(N)-oxalatobis(amino-acidato)cobalt(III) Complexes
Authors: Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Three oxalatobis(amino-acidato)cobalt(III) complexes of a trans(N) type have been resolved into their optically active isomers, and their visible and ultraviolet absorption spectra, circular dichroism spectra, and rotatory dispersion have been measured and discussed. The amino acids used are glycine, β-alanine, and l-α-alanine, the last named of which produces a pair of diastereomeric, not antipodal, isomers in its complex. The two diastereomeric isomers have been separated by means of the solubility difference between them. The splitting of the first absorption band of the complexes has been discussed in relation to the behavior of their CD curves. The absolute configurations of the complexes have been inferred from their CD spectra.
The Chromium(III) Complexes with Ammoniatriacetic Acid. II. The Mixed-ligand Complexes
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following chromium(III) complexes containing ammoniatriacetic acid (ATA) and other reagents as “mixed-ligands” were newly prepared: NH4[Cr(ata) (acac)]·H2O (brown black)(I), [Cr(ata)(o-phen)]·4H2O (brown) (II), [Cr(ata)(dipy)] (red brown)(III), (NH4)2[Cr(ata)·(NCS)2]·H2O (purple black)(IV, and K2[Cr(ata)(ox)]·2H2O(purple)(V), where ata, acac, o-phen, dipy and ox are the abbreviations of the ammoniatriacetate ion, acetylacetone, o-phenanthroline, α,α-dipyridyl, and the oxalate ion respectively. On the basis of the chemical analyses, the thermal analyses, and the measurements of the electronic absorption spectra, it may be considered that ATA was coordinated as a tetradentate ligand in all these complexes obtained. Further information on the conductivity in an aqueous solution suggested that the IV and V complexes are aquated instantly to form the complex ion as [Cr(OH)(ata)(H2O)2]−. The values of the effective magnetic moments for these complexes were 3.7–3.9 B. M., nearly equal to the spin-only values of tervalent chromium.
Synthesis of Chelating Agents. IV. Synthesis and Chelating Behavior of 1-Phenyl-ethylenedinitrilo-N,N,N′,N′-tetraacetic Acid and 1,2-Diphenyl-ethylenedinitrilo-N,N,N′,N′-tetraacetic Acid
Authors: Ôkaku Noboru , Toyoda Kazuho , Moriguchi Yoshiki , Ueno Keihei
Published: July 2006

1-Phenylethylenedinitrilo-N,N,N′,N′-tetraacetic acid and dl-1,2-diphenylethylenedinitrilo-N,N,N′,N′-tetraacetic acid have been synthesized by the carboxymethylation of the corresponding phenyl-substituted ethylenediamines. The chelate stability constants of the two ligands have been determined potentiometrically for alkaline earth and selected transition metal ions. The increase in the chelate stability as compared with EDTA was interpreted in terms of the steric effect of phenyl substitutions.
Kinetic Studies of Bimolecular Nucleophilic Substitution. VII. The Rates of the Menschutkin Reaction of Methyl Iodide with Various Primary, Secondary and Tertiary Amines in Benzene Solvent
Authors: Okamoto Kunio , Fukui Suguru , Nitta Issei , Shingu Haruo
Published: July 2006

The nucleophilicity of a series of primary, secondary and tertiary amines, i. e., methyl-amines, ethylamines, n-butylamines, ethanolamines and benzylamines, has been investigated by following the kinetics of the reaction of these amines with methyl iodide in benzene solvent. The effect of substituents attached to nitrogen atom on the nucleophilicity of these amines is interpreted in terms of the antagonism between steric retardation and inductive effect. The low nucleophilicity observed in the case of tertiary amines is ascribed to the steric retardation at the expense of the inductive acceleration by the substituents. No linear correlation of the nucleophilicity of amines with the pKa values has been observed.
Medium-Sized Cyclophanes. IV. The Halogenation Reactions of [2.2]Metacyclophane
Authors: Sato Takeo , Wakabayashi (née Fujimoto) Meiko , Okamura Yoshio , Amada Teruo , Hata Kazuo
Published: July 2006

It has been postulated that, with proper control and choice of reaction conditions, the halogenation reactions of [2.2]metacyclophane might be directed in either of two ways: (A) the addition-oxidation path or (B) the addition-elimination path. An attempted iodination (iodine-silver perchlorate or iodine chloride) or bromination (bromine-iron catalyst) of [2.2]-metacyclophane resulted in the formation of 4,5,9,10-tetrahydropyrene according to the path B reaction. On the other hand, iodination reaction in the presence of nitric acid has been shown to afford 2-iodo-4,5,9,10-tetrahydropyrene, after path A. Both the reactions have been explained by assuming a common intermediate, which is formed by the attack of the halogenonium ion on one ring, accompanied by a simultaneous transannular attack of the generated phenonium ion on the second ring.
Copolymerization of Vinyl Chloride with Ethylene by Ziegler-Natta Catalysts
Authors: Misono Akira , Uchida Yasuzo , Yamada Kunikazu
Published: July 2006

The copolymerization of vinyl chloride with ethylene by various Ziegler-Natta catalysts was carried out in hydrocarbon solvents at 50°C. On the basis of infrared and NMR spectroscopies of the copolymerization products, it was found that the catalyst systems consisting of Ti(O-n-Bu)4 and alkylaluminums can copolymerize vinyl chloride with ethylene, whereas those consisting of VCl4, VOCl3, Cr(acac)3, Mn(acac)3, or Co(acac)3 and alkylaluminums give polyethylene or a mixture of polyvinyl chloride and polyethylene, and are otherwise inactive. Random copolymers were easily obtained by the use of the Ti(O-n-Bu)4-AlEt2Cl and Ti-(O-n-Bu)4-AlEtCl2 catalyst systems. However, with these catalyst systems, polyethylene was obtained, along with a random copolymer, at a high ethylene feed ratio. This fact indicates the existence of two kinds of active sites, responsible to the copolymerization and the ethylene polymerization respectively. The monomer reactivity ratios were found to be r1(vinyl chloride)=2.0 and r2(ethylene)=0.2 for the copolymerization by either the Ti(O-n-Bu)4-AlEt2Cl or the Ti-(O-n-Bu)4-AlEtCl2 catalyst system. The monomer reactivity ratios are not in agreement with those found in the conventional radical copolymerization. Though the copolymerization reaction was completely inhibited upon the addition of radical inhibitors, this does not seem to support a radical polymerization mechanism directly.
Studies of Antibiotics and Related Substances. XXXII. Syntheses of Neamine and Its Analogue
Authors: Tatsuta Kuniaki , Kitazawa Eiichi , Umezawa Sumio
Published: July 2006

Neamine, an antibiotic glycoside, was synthesized from paromamine. The preferential tosylation of the primary hydroxyl group of tri-N-acetylparomamine was followed by the replacement of the tosyloxy group with an azido group. The azido derivative was catalytically hydro-genated and acetylated to give 4-O-(2,6-diacetamido-2,6-dideoxy-α-d-glucopyranosyl)-N, N-diacetyldeoxystreptamine. De-N-acetylation of the product gave neamine. Furthermore, a structural isomer of neamine, namely 6-O-(3,6-diamino-3,6-dideoxy-α-d-glucopyranosyl)-deoxystreptamine, was synthesized from 6-O-(3-amino-3-deoxy-α-d-glucopyranosyl)-deoxystrept amine which was obtained from kanamycin by partial hydrolysis.
Preparation of Esters of Carboxylic and Phosphoric Acid via Quaternary Phosphonium Salts
Authors: Mitsunobu Oyo , Yamada Masaaki
Published: July 2006

When n-valeric acid was treated with allyl diethyl phosphite and diethyl azodicarboxylate, allyl valeriate and diethyl N-(diethyl)phosphoryl hydrazodicarboxylate were obtained in good yields. Similarly ethyl benzoate was obtained in a nearly quantitative yield by the reaction of benzoic acid with triethyl phosphite and diethyl azodicarboxylate. The reaction of carboxylic acid with triphenyl phosphine and diethyl azodicarboxylate in the presence of an alcohol resulted in the formation of the corresponding esters of the carboxylic acid, triphenyl phosphine oxide, and diethyl hydrazodicarboxylate. The mechanisms of these reactions are also discussed.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. IV. Synthesis and Use of t-Amyl Azidoformate
Authors: Honda Ichiro , Shimonishi Yasutsugu , Sakakibara Shumpei
Published: July 2006

t-Amyl carbazate (II) was synthesized in a satisfactory yield by the direct hydrazinolysis of t-amyl chloroformate (I). Reagent I was prepared by an improved method, using a stock solution of phosgene in toluene. Reagent II was converted to t-amyl azidoformate (III), as in the case of the t-butyl derivative, and reagent III was used for introducing the t-amyloxycarbonyl (AOC) group into free amino acids, amino acid esters, and peptides. Various new AOC-amino acids were synthesized by the present method. Chloroform was found to inhibit the reaction of reagent III with amino acid esters. A practical and safe method for obtaining large quantities of anhydrous hydrazine is described in the present paper.
On the Sn–O Bond in Some Pyridine N-Oxide Complexes of Tin(IV)
Authors: Kawasaki Yoshikane , Hori Mitsufusa , Uenaka Kazushige
Published: July 2006

The stability constants of several pyridine N-oxide complexes of trimethyltin chloride and dimethyltin dichloride have been measured spectrophotometrically in acetonitrile. The values decrease with an increase in the electron-attracting power of the substituent on the pyridine ring. The infrared spectra of several pyridine N-oxide complexes of tin(IV) have been measured from 60 cm−1 to 5000 cm−1. The Sn–O stretching vibration has been observed in the region of 300—400 cm−1, and the frequency depends considerably on the substituents of the tin atom. The Sn–O stretching frequency in the pyridine N-oxide complexes of tin(IV) is rather lower than those in alkyltin alkoxides, which have a large covalent character in the Sn–O bond, but it is higher than those in trialkyltin carboxylates, which have an ionic character in the Sn–O bond. The Sn–O bond in the pyridine N-oxide complexes has been assumed to have a rather large ionic character, from the fact that the dependence of the stability constant on the substituent of the pyridine ring is similar to that of the pKa of the ligand, and from the fact that the frequency of the Sn–O stretching vibration is rather close to that of the trialkyltin carboxylates.
The Photo-ionization of Molecules in Solutions. V. The Mechanism of the Photo-ionization of an Aromatic Diamine in the Polar Media
Authors: Nakato Yoshihiro , Yamamoto Naoto , Tsubomura Hiroshi
Published: July 2006

The photo-ionization of N, N, N′, N′-tetramethyl-p-phenylenediamine (TMPD) in nonpolar solvents was found to occur by the two-step process, with the triplet state as the intermediate. It will be reported here that the photo-ionization of TMPD in polar solvents occurs by the same two-step process, both at 77°K and at room temperature. The flash method was used for the experiments at room temperature. On the other hand, the photo-ionization of TMPD occurs by the single-photon process in ethanol solutions at room temperature when a naphthalene molecule encounters TMPD in the singlet-excited state. The ionization mechanism will be discussed on the basis of these results.
The Crystal and Molecular Structure of Perchloro-(4, 8-dimethylenetricyclo[3. 3. 2. 01,5]deca-2, 6-diene)
Authors: Furusaki Akio
Published: July 2006

The molecular structure of the compound of the formula C12Cl12, mp 273°C, obtained on the pyrolysis of perchloro-(3, 4-dimethylenecyclobutene) at about 250°C, has been determined by a three-dimensional X-ray crystal analysis. The crystal of the compound is monoclinic with four molecules in the unit cell of the dimensions a=16.78, b=6.80, c=17.10 Å and β=116.5°; the space group is C2⁄c. The positions of all the chlorine atoms were elucidated by using the minimum function method, and then those of all the carbon atoms were obtained from an electron density distribution calculated with the phases of chlorine atoms alone. The positional parameters of all the atoms thus obtained were refined by the block-diagonal matrix least-squares method with anisotropic temperature factors. The final discrepancy factor R is 0.094 excluding zero intensity data. As a result of the present study, it is concluded that the compound is perchloro-(4, 8-dimethylene-tricyclo[3.3.2.01,5]deca-2, 6-diene). Except the contacts between the chlorine atoms attached to the same carbon atom, there are several intramolecular Cl···Cl contacts with distances smaller than twice the ordinary van der Waals radius of the chlorine atom; i.e., 3.06, 3.12, 3.13, 3.18 and 3.32 Å. However, it is found that these very close contacts do not seriously affect the bond lengths and angles in the molecule.
Cylindrical Coordinates of Each Atom in a Helical Polymer for a Given Set of Molecular Parameters
Authors: Kijima Hiromasa , Sato Tomohiro , Tsuboi Masamichi , Wada Akiyoshi
Published: July 2006

A method is given for calculating cylindrical-polar coordinates of each atom in a helical polymer from a given set of bond lengths, bond angles, and angles of internal rotation. This should be useful for an analysis of an X-ray fiber diagram of the helical polymer.
Semi-empirical Self-consistent Field Molecular Orbital Calculation of Transition Energy and Oscillator Strength for the Stacked Complexes of Pyrene and 3,4-Benzopyrene with DNA Bases
Authors: Nagata Chikayoshi , Fujita Hiroko , Imamura Akira
Published: July 2006

The transition energy and oscillator strength of stacked complexes of pyrene and 3, 4-benzopyrene with DNA bases are calculated using semi-empirical ASMO SGF CI method, and they are compared with those of free pyrene or 3, 4-benzopyrene. Among the assumed stacking models, the intercalation-like one with guanine reproduced well the experimentally observed red shift and decrease of absorption coefficient in DNA aqueous solution, and this result seems to support the intercalation-like stacking of these hydrocarbons with the DNA bases.
Asymmetric Epoxidation of l-Menthyl Alkylidenecyanoacetates
Authors: Igarashi Minoru , Midorikawa Hiroshi
Published: July 2006

l-Menthyl alkylidenecyanoacetates have been prepared. The reaction of the esters with hydrogen peroxide in the presence of a base is accompanied by a partial asymmetric synthesis, as is shown by the hydrolysis of the resulting epoxy esters to epoxy acids.
The Synthesis of Carrabiose
Authors: Hirase Susumu , Araki Choji
Published: July 2006

Carrabiose (3, 6-anhydro-4-O-β-d-galactopyranosyl-d-galactose) was synthesized by a series of reactions involving the condensation of methyl 2-O-p-tosyl-3, 6-anhydro-α-d-galactopyranoside with tetra-O-acetyl-α-d-galactopyranosyl bromide, followed by deacetylation, detosylation, and removal of the glycosidic methoxyl group. From the resulting disaccharide, several crystalline derivatives were prepared. All of these derivatives were identical in every respect with the corresponding compounds, which had been obtained from natural sources.
The Synthesis of N-Methylnupharamine
Authors: Matsutani Shigeru , Kawasaki Ichiro , Kaneko Takeo
Published: July 2006

Studying the synthesis of nupharamine, a minor alkaloid isolated from Nuphar japonicum DC, N-methylnupharamine was synthesized and its stereoisomers were characterized.
Synthetic Studies of Bacitracin. II. Synthesis of a Cyclic Dodecapeptide, an Analogue of Bacitracin A
Authors: Ariyoshi Yasuo , Shiba Tetsuo , Kaneko Takeo
Published: July 2006

For the purpose of making a total synthesis of bacitracin A, a protected heptapeptide with a ring structure, Nα- (formyl-l-isoleucyl)-cyclo-(l-lysyl-δ-tosyl-d-ornithyl-l-isoleucyl-d-phenyl-alanyl-im-benzyl-l-histidyl-α-methyl-β-l-aspartyl) was first prepared by a high dilution method. After deformylation, it was coupled with a tetrapeptide corresponding to the N-terminal part of bacitracin A, the benzyloxycarbonyl-l-isoleucyl-S-benzyl-l-cysteinyl-l-leucyl-d-glutamic acid (α-azide)-γ-t-butyl ester, to afford an undecapeptide derivative. This was converted to a hydrazide, which was then coupled with β-benzyl-d-isoasparaginate to give the Nα-(benzyloxycarbonyl-l-isoleucyl-S-benzyl-l-cysteinyl-l-leucyl-γ-t-butyl-d-glutamyl-d-isoleucyl)-cyclo-(l-lysyl-δ-tosyl-d-ornithyl-l-isoleucyl-d-phenylalanyl-im-benzyl-l-histidyl-β-l-aspartyl)-d-isoasparagine β-benzyl ester. The removal of all protecting groups from it gave a free dodecapeptide, which has the same amino acid sequence, including optical properties, as that of the structure of bacitracin A proposed by Stoffel and Craig; it is different from the latter only in having the thiazoline ring replaced with the cysteine residue. The synthetic dodecapeptide was tested for biological activity and for the formation reaction of the thiazoline ring.
The Influence of Agitation on the Gas-phase Ethylene Polymerization Induced by γ-Rays
Authors: Kawakami Waichiro , Hagiwara Miyuki , Hosaki Yoshihiko , Machi Sueo , Kagiya Tsutomu
Published: July 2006

The effect of agitation on the γ-ray induced polymerization of ethylene was studied in a gaseous system at a pressure of 400 kg/cm2 and at a temperature of 30°C, with dose rates ranging from 9.0×102 to 3.8×105 rad/hr. Both the rate and the degree of polymerization decreased upon agitation to I. 50% of those in the polymerization without agitation. The kinetical analysis of the experimental results has shown that this decrease in the rate and in the degree of polymerization is mainly due to a decrease in the absolute propagation rate. Further, it was found that agitation has no effect on initiation and transfer reactions. The termination was not effected by agitation under a high dose rate, but it was slightly promoted at lower dose rates.
The Ultrasonic Study of Aqueous Solutions of Urea
Authors: Arakawa Kiyoshi , Takenaka Nobuo
Published: July 2006

An ultrasonic investigation of aqueous solutions of urea was made by means of the pulse technique. The ultrasonic velocity and absorption were measured on solutions of about 14– 43 wt% in the frequency range from 5 to 45 Mc/sec. In an 8 m urea solution the velocity vs. the temperature curve was found to be horizontal in the temperature range from 20 to 40°C. The α/f2vs. logf curves (α, absorption coefficient; f, frequency) showed a very small frequency dependence throughout this experiment. The magnitude of α⁄f2 first decreases upon the addition of urea; at about 4–6 m of urea it reaches a shallow minimum, thereafter slowly increasing. At about 8 m of urea the contribution to the ultrasonic relaxation from the open-packed structure in water completely disappears, and the contribution from the water-urea structure as well as that from the association of urea is small.
Intensities of the T←S Transitions in Oxalyl Chloride and Bromide
Authors: Shimada Hiroko , Kanda Yoshiya
Published: July 2006

The matrix elements of the spin-orbit interaction and the intensities of the T←S transitions resulting from possible perturbing processes in glyoxal and its halogen substituted derivatives are examined. The calculated results show that the T←S transitions in these molecules borrow their intensities predominantly from the 1Bu(π,π*)←1Ag and 3Bg(n,π*)←3Au transitions by means of the first-order spin-orbit interaction. An experimental study of the T←S absorptions of haloderivatives of glyoxal shows that the intensity increases with an increase in the atomic number of the halogen atom. This intensification due to halosubstitution can be interpreted in terms of two factors; (1) the halosubstitutional effects on the transition energies and on the intensities of these two perturbing transitions, and also on the transition energy of the T←S transition, and (2) the halosubstitutional effect on the matrix element of the spin-orbit interaction, which comes to involve the one-center term on the halogen atom if slight delocalizations of the n-orbital as well as of the π-orbital over the halogen atom are taken into account.
Semi-Empirical SCF MO Treatment for Valence Electron Systems. Electronic Structures of trans- and cis-Isomers of Butadiene, Acrolein, and Glyoxal
Authors: Kato Hiroshi , Konishi Hideyuki , Yamabe Hiroko , Yonezawa Teijiro
Published: July 2006

Using a semi-empirical ASMO SGF method for all valence electron systems, but a method modified to include one-center exchange integrals and an off-diagonal core integral as estimated by the approximation in our previous treatment, the electronic structures of trans- and cis-isomers of butadiene, acrolein, and glyoxal are calculated. The energy sequence of the molecular orbitals, the charge distributions in lone-pair orbitals and π MO’s, and the charge distribution in these compounds are investigated. The n–π* and π–π* transition energies are also presented; the agreement between the calculated and observed values is almost entirely satisfactory. Further, the singlet-triplet oscillator strength in the trans-glyoxal is estimated by means of the obtained results.
The Measurement of Surface Excess Oxygen of Nickel Oxide Catalysts by Reduction with Hydrazine
Authors: Uchijima Toshio , Takahashi Masamichi , Yoneda Yukio
Published: July 2006

The method for the determination of the surface excess oxygen of oxides has been provided by using aqueous hydrazine solution as a reducing reagent and applied to several pure and lithium doped nickel oxide catalysts, calcined at various temperatures from 350 to 900°C. Two different kinds of procedures, i. e., titration of the amount of hydrazine consumed and volumetric measurement of gaseous nitrogen evolved, have been employed. A satisfactory agreement is obtained between both methods, which affirms that the following reaction is taking place.

N2H4+2O(S)→N2+2H2O

The amount of the surface excess oxygen decreases monotonously with increasing calcination temperature and also with increasing concentration of the lithium oxide additives. From comparison of these results with those due to acidic chloride and iodide methods, most of the excess oxygen is concluded to exist on the surface of the oxides and, furthermore, a certain distribution in the oxidation power of the excess oxygen is suggested to exist.
The C-C Bond Rupture in the Radiolysis of Liquid n-Hexane
Authors: Shinsaka Kyoji , Shida Shoji
Published: July 2006

The effects of added N2O, NO, N2O-NO mixture and NH3 on the yields of fragment products of n-hexane in the γ-radiolysis of liquid n-hexane at 40°C have been investigated. All of these additives decrease to a certain extent the G-values of fragment products. The decreases of the G-values at sufficiently high N2O concentration (∼0.3 mol/l) are approximately the same as those in the presence of NH3. The degrees of contribution of neutralization process and other processes to the C-C bond rupture have been separately estimated from the decreases at sufficiently high concentration of N2O, NO and N2O-NO mixture. It is shown that processes other than neutralization may play rather an important role than neutralization in the C-C bond rupture. The effect of added NH3 on the yields of fragment products of n-hexane may be attributable to either the proton transfer from n-C6H14+ to NH3 or the charge transfer from n-C6H14+ to NH3.
A Spectrophotometric Study of the Thorium Complex of 2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-mandelic Acid
Authors: Miyata Haruo
Published: July 2006

2-(1, 8-Dihydroxy-3, 6-disulfo-2-naphthylazo)-mandelic acid forms a stable violet complex with thorium ion at 1:1 molar ratio in an acidic solution. The acid dissociation constants of the reagent and the apparent stability constant of its thorium complex were estimated spectrophotometrically at 25°C and μ=0.1. It was found that the thorium complex formed by the present reagent was more stable than those of the other phenyl-azo-chromotropic acid derivatives reported in the preceding papers.
Studies of Mixed Cyano Cobalt(III) Complexes. III. Some Cis Isomers of Monocyanobisethylenediamine Series
Authors: Ohkawa Kuwako , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Five new cis isomers of the [Co(X)(CN)en2]n+ complexes, namely, those of X=NH3, OH2, OH−, I− and NO2−, have been prepared and resolved into their optically active isomers. A new trans isomer of X=NO2− has also been prepared. The splitting of the d→d absorption bands of the geometrical isomers of the [Co(X)(CN)en2]n+ complexes have been discussed in reference to their visible and ultraviolet absorption spectra, rotatory dispersion and circular dichroism spectra.
Synthetic Studies Starting from β-Cyanopropionaldehyde. IV. Reactions of β-Cyanoacrolein
Authors: Satsumabayashi Sadayoshi , Motoki Shinichi
Published: July 2006

The reactions of β-cyanoacrolein or its dimethyl acetal were investigated. Various new compounds were prepared by the application of several basic reactions, namely, oxidation, reduction, addition, and others. Moreover, β-cyanoacrolein was found to react as a dienophile or as a diene in Diels-Alder reactions. In the reaction with butadiene, isoprene, and 1, 3-pentadiene, cyanotetrahydrobenzaldehyde derivatives were obtained. When ethyl vinyl ether or butyl vinyl ether was used as a dienophile, dihydropyran derivatives were prepared; this pyran was hydrolyzed with dilute hydrochloric acid to 2-cyanoglutar aldehyde.
On the Formation of Benzonitrile from Benzaldehyde and Ammonia. II. Iodine as an Oxidant
Authors: Misono Akira , Osa Tetsuo , Koda Seiichiro
Published: July 2006

The present authors previously reported a method of synthesizing nitriles from aldehydes by using iodine as an oxidant (Bull. Chem. Soc. Japan,  39, 854 (1966)). The possible route and detailed conditions of this reaction have now been investigated in the case of benzaldehyde; the results will be described in this paper. Benzaldehyde, ammonia, and iodine in methanol react to form benzonitrile and methyl benzoate as the main products. A possible reaction mechanism is suggested by a consideration of the effect of the temperature and of the concentrations of the reactants, and of the effect of the addition of ammonium iodide and water, as well as by a consideration of the results of the reaction starting from hydrobenzamide. The mechanism may be as follows. Iodamine, which is in equilibrium with iodine and ammonia, oxidizes benzilideneimine, which arises from the reaction between benzaldehyde and ammonia to give hydrobenzamide, to produce benzonitrile. Methyl benzoate is produced by the oxidation of the hemiacetal which arises from the reaction between benzaldehyde and methanol. Gyaphenin (2, 4, 6-triphenyl-1, 3, 5-triazine) is found as a by-product, but it is shown not to be produced by the trimerization of benzonitrile.
Kinetic Studies of the Photoreaction of Benzophenone with Furan
Authors: Toki Susumu , Sakurai Hiroshi
Published: July 2006

The photoreaction of benzophenone with furan was studied kinetically in a benzene solution. A reaction mechanism was proposed, and the rate constants of elementary reactions were determined. Benzophenone gives primarily oxetane with furan through the n-π* lowest triplet state. Benzophenone reacts with the oxetane initially formed to afford a 2 : 1-adduct or to decompose that to the starting materials. The ratio of the addition to the decomposition is 1 : 4. The simplest scheme for the direct cycloaddition of a benzophenone triplet and an alternate scheme involving a biradical intermediate are discussed; the second scheme is more acceptable. The rate of the formation of the intermediate is considerably slower in a benzophenone-furan system than in a benzophenone-ketenimine system (ca. 1/10). The formation of oxetane is greatly dependent on the ratio of the bond-forming to the bond-breaking of the biradical intermediates, which are efficiently formed (4.2×107  m−1 sec−1 for furan and 4.0×107  m−1 sec−1 for oxetane).
Über die Darstellung einiger 5-Oxo-2-methyl-4, 4-dialkyl-3-äthoxycarbonyl-4, 5-dihydroindol und deren Reduktionen
Authors: Suehiro Tadashi , Sugimori Shigeru
Published: July 2006

Direkte 4-Alkylierung von 5-Hydroxy-2-methyl-3-äthoxycarbonylindol (I) verläuft mit Cinnamylchlorid ausser mit Benzyl- und Allyl-chlorid, aber nicht mit Benzyloxymethylchlorid, Chloracetonitril, Bromessigester und Bromacetal. 4-Allylindol-Derivat IIb lässt sich auch durch Claisen-Umlagerung von 5-Allyloxyindol-Derivat IIIa herstellen. In Kombination der C-Benzylierung, C-Allylierung und der katalytischen Hydrierung mit der Claisen-Umlagerung kann man einige 5-Oxo-2-methyl-4, 4-dialkyl-3-äthoxycarbonyl-4, 5-dihydroindole IV darstellen. Beim Erhitzen von 5-Oxo-4, 4-diallyl-Verbindung IVb findet eine Umlagerung in 5-Hydroxy4, 6-diallyl-Derivat IIe statt, dessen Struktur synthetisch festgestellt wurde, während beim 5-Oxo-4,4-dibenzyl-Derivat IVa eine Benzyl-Gruppe unter Aromatisierung abgespaltet wird. Katalytische Hydrierung und Natriumborhydrid Reduktion von IV wurden mit einander vergleichend untersucht.
Silent Discharge Reactions in Aqueous Solutions. IV. Systems of Ferrous-Cupric Ions and Ceric-Thallous Ions Acidified with 0.8 n Sulfuric Acid in Helium and Argon Atmospheres
Authors: Yokohata Akira , Tsuda Satoru
Published: July 2006

In this series of studies of silent discharge reactions, the G values of the hydrogen atom,, the hydroxyl radical and hydrogen peroxide have successfully been determined in terms of the radiolysis of water by slow electrons: G(H)=1.1, G(OH)=1.6, and G(H2O2)=1.0 in helium, and G(H)=0.6, G(OH)=0.7 and G(H2O2)=1.5 in argon. Also, the absorbed dose has been estimated. In order to obtain further information regarding the nature of these radicals and the adequacy of these G values, the ferrous-cupric ions system and ceric-thallous ions system in atmospheres of helium and argon have now been investigated. The experimental results show that Gobs(Fe3+) in a ferrous-cupric ion system and Gobs(Ce3+) in a ceric-thallous ion system almost coincide with Gcalc(Fe3+) (=2G(H2O2)+G(OH)–G(H)) and Gcalc(Ce3+) (=2G(H2O2)+G(OH)+G(H)), as was to be expected from the previously determined G values. These findings suggest that the silent discharge reaction in these systems can be well interpreted in terms of the scavenging effect of cupric ions and thallous ions on the hydrogen atom and the hydroxyl radical, as in the case of radiation chemistry. Further, the present study has confirmed that the G values determined in the earlier experiment are reliable.
An ESR Study of the Aromatic-compounds-photosensitized Decomposition of Alcohol by the Two-photon Process
Authors: Shimokoshi Kazuo , Mori Yuji , Tanaka Ikuzo
Published: July 2006

ESR techniques were used to examine the photosensitized decomposition of solvents in a system composed of α-naphthol and its derivatives, diphenylamine, tetraphenyl hydrazine, and diphenyl methane in methanol, EPA, and ethanol at 77°K. The effects of intermittent irradiation and incident light intensity were investigated mainly in the system composed of α-naphthol in methanol at 77°K. The lifetime of the lowest triplet state of α-naphthol was determined by the intermittent irradiation, with some kinetic considerations; it agreed reasonably well with the values obtained by the direct measurement of the phosphorescence. The rate of the radical formation was found to be nearly proportional to the square of the light intensity. From these results, it was concluded that T-T* absorption in these sensitizers played an important role in forming the radicals from alcohols. The inter-molecular triplet-triplet energy transfer process was also confirmed in a system composed of a mixed alcoholic solution of phenanthrene and naphthalene at 77°K.
The Electronic and ESR Spectra of Triphenylmethane Adsorbed on Solid Acid Catalysts
Authors: Arai Hiromichi , Saito Yasukazu , Yoneda Yukio
Published: July 2006

The electronic spectra of adsorbed triphenylmethane have been observed through a study of disk samples made by the compression method from ordinary powder catalysts. Three kinds of adsorbed species of triphenylmethane were obtained for silica-alumina. The band at 265 mμ was due to a physically adsorbed species (Ph3CH). A new band at 340 mμ was assigned to the triphenylmethyl radical (Ph3C·), formed in the absence of air, with a sharp spectrum (g=2.004) observed in the electron spin resonance. The species of the bands at 408 and 435mμ was identified as triphenylcarbonium ion (Ph3C+), the amount of which increased with the light and temperature exposure period. Types of acid present on silica-alumina, alumina, silica, and other catalysts were discussed.
Electric Conductivity and Viscosity Studies of Aqueous Solutions of Nitroamminecobalt(III) Complexes
Authors: Tamamushi Reita , Isono Toshiaki , Katayama Shunzo
Published: July 2006

The ionic equivalent conductivities at infinite dilution, viscosity B-coefficients, partial molal volumes, and ionic radii of nitroamminecobalt(III) complex ions have been determined in aqueous solutions at 25 °C. From the conductivity data, the thermodynarnic association constants of the polyvalent complex cations with chloride ions have been calculated. The log K values at 25°C are 1.5 for [Co(NH3)6]3+–Cl− and 1.3 for [Co(NO2)(NH3)5]2+–Cl− respectively. Some factors, which will determine the B-coefficients of complex ions, have been briefly discussed.
The Oxidation of the Methyl Group at C-5 in Friedelin and Shionone
Authors: Fukuda Toshio , Tsuyuki Takahiko , Tanahashi Yoshiaki , Takahashi Takeyoshi
Published: July 2006

3β-Friedelanol (V, R=H) and 3β-shionanol (VIII, R=H) have been converted into γ-lactones, (VI) and (IX) respectively, either by lead tetraacetate-iodine oxidation followed by Jones’ oxidation or by photolysis of their nitrites (V, R=NO and VIII, R=NO) followed by Jones’ oxidation. These results confirm the presence of an axial methyl group at C-5 in friedelin (II) and shionone (I).
α-Pyrone-6-carboxylic Acid Derivatives. IV. Optical Resolution and Configuration of Stizolobic Acid, Stizolobinic Acid and β-(6-Carboxy-α′-pyron-5-yl)alanine Lactam
Authors: Senoh Siro , Maeno Yoshiko , Imamoto Shoji , Komamine Atsushi , Hattori Shizuo , Yamashita Kyohei , Matsui Masanao
Published: July 2006

The optical resolution of three isomers of Dl-β-(6-carboxy-α′-pyronyl)alanine was carried out by chemical as well as enzymatic methods and six optically active isomers were obtained. The configuration of each aspartic acid, derived from the ozonolysis of these optical isomers in aqueous solution, was analyzed enzymatically using glutamic-oxaloacetic transaminase and malate dehydrogenase. By the same procedure, the configuration of the two natural amino acids, stizolobic acid and stizolobinic acid, was confirmed and both were assigned the L-form. Thus the absolute configuration of six optical active isomers of β-(6-carboxy-α′-pyronyl)alanine and the two natural amino acids is assigned unequivocally, and the relationship between the synthetic and the natural amino acids is established.
The Photo-Ionization of Molecules in Solutions. IV. Electron Capture and Charge Transfer Fluorescence Phenomena Occurring between N, N, N′, N′-Tetramethyl-p-phenylenediamine and Electron Acceptors in Organic Solvents
Authors: Yamamoto Naoto , Nakato Yoshihiro , Tsubomura Hiroshi
Published: July 2006

A mixture of N, N, N′, N′,-tetramethyl-p-phenylenediamine (TMPD) and pyrene in some rigid matrices was illuminated at a low temperature in the near ultraviolet region. It was found that TMPD+, pyrene anion, and solvated electrons are formed in the medium. The ratio of the formation of pyrene anion and TMPD+ has been studied at various concentrations of pyrene. The behavior of the photo-ejected electron, particularly its extent of migration has then been discussed on the basis of the experimental results. The thermoluminescence spectrum of the UV-irradiated matrix containing TMPD and pyrene was measured after it had been illuminated in the infrared region. The luminescence may tentatively be assigned to the charge transfer fluorescence. The emission spectra were investigated for a mixture containing TMPD and α-methylnaphthalene in several solvents by exciting the TMPD. It was found that a new emission band appeared at 480 mμ. It was assigned to the charge transfer fluorescence.
Electronic Structures and Reactivities of Aliphatic Small-Membered-Ring Compounds. I
Authors: Yonezawa Teijiro , Shimizu Kiyoshi , Kato Hiroshi
Published: July 2006

Extended LCAO MO investigations into the physico-chemical properties of cycloalkanes and their derivatives are carried out. The bond natures of C–C and C–H in cycloalkanes, the electronic distributions of the lowest vacant orbital, the electron-attracting powers of the ring, and the relative reactivity of the ring cleavage are successfully explained. Further, their ionization potentials and electron affinities are discussed. In addition, the electronic distributions on the equatorial and axial forms of monosubstituted cyclobutane and cyclohexane are made explicit.
Studies of the Photochemistry of Aromatic Diazo Compounds. I. Electronic Structure and Photodecomposition of Benzenediazonium Salt
Authors: Sukigara Mitsunori , Kikuchi Shin-ichi
Published: July 2006

The electronic states of benzene diazonium cation were calculated by a method similar to that of Pariser and Parr. On the basis of the calculations, the 259 mμ and 295 mμ absorption bands were attributed to 1A1–1A1 and 1A1-1B1 transitions respectively. When the sample was irradiated in an alcoholic solution by a 295 mμ light, no ESR signal was detected, but fluorescence and phosphorescence were observed; the fluorescence and the absorption spectrum of 1A1–1B1 transition have the correlation of a mirror image to each other. On the other hand, upon irradiation by a 259 mμ light, this sample showed an ESR spectrum which was attributed to the phenyl σ-radical, but no fluorescence or phosphorescence was observed. From the above experimental results and theoretical considerations, it was concluded that the electronically-excited benzenediazonium salt releases its excess energy by the following processes: (1) From the excited 1B1 state, there occur radiative transition to the ground state and intersystem crossing to the phosphorescent state, though it is as yet uncertain whether 3B1 or any other triplet states are involved. The photodecomposition does not proceed from the excited 1B1 state. (2) From the excited 1A1 state, neither the radiative transition to the ground state nor a nonradiative transition to any fluorescent or phosphorescent states occurs. The molecule decomposes rapidly to give phenyl σ-radical after excitation to this electronic state.
Phase Transitions in Poly-n-Alkyl Methacrylate Monolayers
Authors: Nakahara Tatsuo , Motomura Kinsi , Matuura Ryohei
Published: July 2006

The effects of temperature on the surface pressure of monolayers of polymethacrylates with n-alkyl groups containing from 9 to 18 carbon atoms have been studied. Two kinds of phase transitions have been observed in the surface pressure-area isotherms. On the basis of the bulk properties of the polymers, these phase changes have been interpreted as the transition of the monolayer to a three-dimensional fluid state and as side-chain crystallization.
Chlorine Nuclear Quadrupole Resonance Study of the Molecular and the Ionic Crystals of Phosphorus Pentachloride and the Phase Transitions in and between the Two Crystalline Modifications
Authors: Chihara Hideaki , Nakamura Nobuo , Seki Syûzô
Published: July 2006

The 35Cl quadrupole resonance (NQR) spectra in both the molecular (PCl5) and the ionic (PCl4+·PCl6-) solid modifications were measured and assigned, and their temperature dependences (20 to 250°K) were interpreted by a modified Bayer theory. A phase transition of higher order occurs in the ionic solid at 102.3°K which was also revealed by a preliminary heat capacity measurement: There are seven resonance lines below 102.3°K and four above it. An anisotropy in the librational motion is suggested. The molecular solid modification is metastable and transformation into the ionic solid occurs over a range of temperature. This was observed both in the quadrupole resonance spectrum and in the differential thermal analysis; the latter was used to derive the apparent activation energy for the disproportionation reaction. A phase transition occurs also in the molecular solid at 183°K. The partial ionic character of the P-Cl bonds in the two modifications was estimated from the NQR results and could account for the observed chemical shift in the nuclear magnetic resonance of 31P. The 35Cl resonance frequencies in a family of compounds PXn were correlated.
The Crystal Structure of trans-Diaquo-bis(pyridine-2-carboxamide)-nickel(II) Chloride, [Ni(H2O)2(piaH)2]Cl2
Authors: Masuko Akiyoshi , Nomura Teruo , Saito Yoshihiko
Published: July 2006

The crystal structure of trans-diaquo-bis(pyridine-2-carboxamide)nickel(II) chloride, [Ni-(H2O)2(piaH)2]Cl2, was determined by X-ray diffraction and refined by three-dimensional least-squares method. The crystals are monoclinic with space group P21⁄a, a=13.567, b=10.067, c=6.355 Å and β=113.73°. There are two formula units in the unit cell. The structure is built up of centrosymmetric complex ions and chloride ions. Two ligand molecules are coordinated to the nickel atom in trans position with amide oxygen atoms and ring nitrogen atoms. (Ni–N, 2.02 Å, Ni–O, 2.05 Å). The ligand molecules are nearly planar and they are approximately in one plane with the nickel atom. Two water molecules are coordinated at a distance of 2.14 Å and complete the octahedral arrangement around the nickel atom.
The Changes in the Secondary Properties of Zinc Oxide in the Process of Mechanical Treatment
Authors: Takahashi Hiroshi , Tsutsumi Kazuo
Published: July 2006

The changes in the secondary properties of zinc oxide upon mechanical treatment were studied. In the process of the mechanical treatment of zinc oxide, the Blaine specific surface area, the sedimentation volume, and the particle size distribution changed periodically with the treatment time. Such periodical changes are characteristic of the state of association of the particles, and can be interpreted as the changes in the total energy content of the solid.
Kinetic Studies of Thermal Decomposition Reactions of Metal Complexes. Hexammine- and Halogenopentamminecobalt(III) Complexes
Authors: Tanaka Nobuyuki , Nagase Kenzo
Published: July 2006

The thermal decomposition reactions of amminecobalt(III) complexes in solid state were studied mainly by the polarographic, the manometric and the infrared spectroscopic methods. The decomposition processes of [Co(NH3)6]Cl3, [Co(NH3)6]Br3, [Co(NH3)6]I3, [CoCl(NH3)5]Cl2, [CoBr(NH3)5]Cl2, [CoCl(NH3)5]Br2 and [CoBr(NH3)5]Br2  in vacuo, in air atmosphere and in sealed tube were investigated. In all cases, the decomposition of these complexes was initiated by electron transfer from an outer-sphere anion or a ligand to the central cobalt(III) cation. The reaction processes and products were found to be much different with the different environments, but little different with the different halide ions. The rate constants, frequency factors and activation energies for the electron transfer reactions were obtained.