bluuebunny/crossref_metadata_2025 huggingface dataset:
A Comparison of 4-Hydroxynaphthalene-2,7-disulfonic Acid with Chromotropic Acid as a Coupling Component of Azo type Metallochromic Indicators
Authors: Katayama Takeshi , Miyata Haruo , Tôei Kyoji
Published: July 2006

In order to clarify the effect of the hydroxyl group at the 5-position of chromotropic acid on the chelate stabilization, the following six reagents were synthesized by the coupling with 4-hydroxynaphthalene-2,7-disulfonic acid or 4,5-dihydroxynaphthalene-2,7-disulfonic acid(chromotropic acid): 2-(m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(I), 2-(o-methoxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(II), 2-(o-hydroxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(III), 2-(m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(IV), 2-(o-methoxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(V), and 2-(o-hydroxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(VI). The acid dissociation constants of these reagents and the stability constants of their metal chelates with magnesium and calcium were measured by the pH titration method at an ionic strength of 0.10 and at 25°C. From the results obtained, it has become apparent that the hydroxyl group at the 5-position exerts a remarkable influence on the chelation of metal ions with the bidentate ligand, such as 2-(m-sulfophenylazo)-chromotropic acid, but that it has very little effect on those ions with the terdentate ligand, such as 2-(o-hydroxy-m-sulfophenylazo)-chromotropic acid. Such an effect appears even in the bidentate ligand with the methoxy group at the ortho-position of the benzene ring. That is to say, it may be concluded that the effect of the number of the chelate ring formed with a metal ion is preferred to stabilize the metal chelate over the effect of the hydroxyl group at the 5-position in the terdentate ligand.
The Separation of Copper Isotopes by Ion-exchange Chromatography
Authors: Kanzaki Tadao , Kakihana Hidetake
Published: July 2006

A break-through experiment on the separation of copper isotopes was carried out through the use of a cation-exchange resin column. By analysing the experimental results, the approximate values of the single-stage (elementary) separation factors, S6563, were determined. The copper sulphate and copper chloride systems gave significant separation factors (S6563=1.00003–1.00042), but the copper nitrate system gave no isotope separation. These data were analysed in terms of the theory of the two-phase distribution of isotopes previously proposed by one of the present authors (Kakihana). The equilibrium coefficient for isotopic-exchange reaction by complex formation in an external solution (K1=1.00015 for the copper sulphate system, and K1=1.0005 for the copper chloride systems) was estimated.
Metal Complexes Containing Six-Membered Chelate Rings. I. Preparation and Structure of 2,4-Pentanediaminetetraacetato Complexes of Cobalt(III)
Authors: Mizukami Fujio , Ito Haruko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

New cobalt(III) complexes with 2,4-pentanediaminetetraacetate (2,4-ptnta4−) have been prepared. The optically active 2,4-ptnta4− (RR or SS) forms a sexadentate complex and determines the absolute configuration around the metal ion. The meso-2,4-ptnta4− (RS) coordinates to the metal ion as a quinquedentate with a free acetate branch. Such stereospecific formations of sexa- and quinquedentate complexes from the optically active and the meso 2,4-ptnta4− have been attributed to the steric regulation coming from the methyl groups on the α-carbon atoms.
Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. IV, The Reaction in Mixed Solvents of Dimethyl Sulfoxide and Water
Authors: Wada Goro , Aoki Michiko
Published: July 2006

The rate constants, kapp, of the electron transfer reaction between iron(II) and iron(III) in mixed solvents of DMSO and water were measured at various acid and DMSO concentrations at μ=0.50m and 25°C. The kapp decreased linearly with the increase in [DMSO] at a constant [H+] and increased linearly with the increase in 1/[H+] at a constant [DMSO]. The reaction is considered to proceed through two paths: Fe2++*Fe3+→Fe3+*Fe2+ and Fe2++*FeOH2+→FeOH2++*Fe2+, with the rate constants of kO and kH respectively. Both kO and kH were suppressed by the addition of DMSO to water because of the occurrence of molecular association between DMSO and water. The hydration number of DMSO in a very dilute aqueous solution was approximately six, as revealed by the cryoscopic measurements. The suppression of kO and kH was proportional to [DMSO], with a common proportional constant. Consequently, DMSO was deduced to destroy the chains of water molecules connected by hydrogen bondings and to interfere with the ease of hydrogen atom transfer between the reducing and oxidizing iron species. DMSO itself did not serve as a ligand to catalyze the reaction as N-methylacetamide, N,N-dimethylacetamide, and various other anions do.
Mass Spectrometry of Dyes. IV. Electron Impact Reaction of Nitrophenyl Phenyl Ethers and Their Charge Migration
Authors: Yamada Kazutoshi , Konakahara Takeo , Iida Hirotada
Published: July 2006

By the electron impact reaction of substituted 4-nitrodiphenyl ethers (1), the substituents on ring B of (1) cause a reasonable change in the intensity of fragment ions which result from the nitro→ nitrite ester rearrangement. There is a linear correlation of the M+–NO fragment ion intensity of (1) with the ionization potential of the molecules, and with Hammett σ constants. These evidences suggest that the charge of ring B will be free to migrate to ring A in the ion state, even if they are separated by O-atom.
The Reactions of Pyridinium Bromides with Sulfenamides
Authors: Mukaiyama Teruaki , Saigo Kazuhiko
Published: July 2006

It was found that three different types of products, phenylthiomethylpyridinium bromide, ethoxy-bis(phenylthio)-methane and ethyl ethoxy-bis(phenylthio)acetate were obtained by the reactions of pyridinium bromides, such as phenacylpyridinium bromide, acetonylpyridinium bromide and ethoxycarbonylmethylpyridinium bromide, with sulfenamides in ethanol, depending on the nature of the carbonyl carbon of the starting pyridinium bromides.
Group Interactions in Polyelectrolytes. IV. Kinetics of the Alkaline Hydrolysis of Polymethyl Acrylate (Part II)
Authors: Kawabe Hiroshi , Yanagita Masaya
Published: July 2006

Rate equations which express the over-all kinetics of the alkaline hydrolysis of polymethyl acrylate in the presence of a large excess of alkali were derived. The over-all course of this reaction was calculated by using the rate constants given in the previous paper, which were derived from the kinetic data obtained by the reaction in a 29% (v/v) aqueous acetone solution with a slight excess of sodium hydroxide at 55°C. The partially-hydrolyzed polymethyl acrylate (30.6% hydrolyzed) was hydrolyzed by the addition of about sixteen times as much sodium hydroxide as the amount of the ester group; the kinetic data thus obtained were found to be in good agreement with the calculated values.
The Photoreactions of Phenazines via a Semiquinone Radical. The Photoreductive Deacylation of 1- or 2-Acyloxyphenazine
Authors: Inoue Hiroo , Ochiai Tadao , Sugimoto Akira , Imoto Eiji
Published: July 2006

The Photo-irradiation of a solution of 1- or 2-benzoyloxyphenazine in 2-propanol, followed by aeration, affords 1- or 2-hydroxyphenazine, benzaldehyde, isopropyl benzoate, and/or benzoic acid as the reaction products. The spectral change of the solution in the reaction process gives evidence of the fission of the acyl-to-oxygen bond. The addition of ferric chloride or dimethyl sulfate to the reaction system containing 1-benzoyloxyphena-zine in 2-propanol leads to the formation of isopropyl benzoate. When methanol instead of 2-propanol is used as the solvent, methyl benzoate is produced mainly. In cyclohexene as a hydrogen-donating solvent, benzaldehyde and an oxetane are obtained. The irradiation of a solution of 1-benzoyloxyphenazine in t-butyl alcohol or benzene gives no product, and the starting material is recovered in a 90–100% yield. 1-Benzoyloxyphenazhydrin, a photo-reduction intermediate, does not contribute to the formation of benzaldehyde. The intermediary formation of a semiquinoid form during irradiation brings about the fission of the acyl-to-oxygen bond, thus affording the corresponding aldehyde.
Studies on the Baudisch Reaction. IV. The Reaction Mechanism
Authors: Maruyama Kazuhiro , Tanimoto Iwao
Published: July 2006

Mechanism of the Baudisch reaction was investigated using semicarbazide hydrochloride in lieu of hydroxylamine hydrochloride which is one of the reacting components. It was suggested that pyrocatechol-copper-hydroxylamine complex formed as a reaction intermediate is oxidized to o-benzoquinone-copper complex by hydrogen peroxide and one of the carbonyl groups of o-benzoquinone reacts with hydroxylamine hydrochloride to give o-benzoquinone monooxime, i.e. 2-nitrosophenol.
Retardation Effect Induced by Pyridine in the Radical Copolymerization of Styrene and Liquid Sulfur Dioxide
Authors: Enomoto Tsutomu , Iino Masashi , Matsuda Minoru , Tokura Niichiro
Published: July 2006

We have found that the radical copolymerization of styrene and liquid sulfur dioxide (liq. SO2) is retarded when a basic solvent such as pyridine is used; we also investigated the mechanism of the retardation induced by pyridine. The polymerization in pyridine was most strongly retarded when the styrene mole fraction in the feed, [St]0/ ([St]0+[SO2]0), was small (below about 0.2) and when the pyridine mole fraction in pyridine-liq.SO2, [Py]0/ ([Py]0+[SO2]0, was 0.4–0.5. Moreover, from the results in the reaction of the phenylsulfonyl radical (the model radical for the propagating sulfonyl radical) in pyridine or in a pyridine - liq. SO2 mixture, it may be concluded that the end unit of the polymer has the pyridinium sulfonate structure (–SO3−HPy+) and that the retardation may occur by means of the reaction of the propagating sulfonyl radical with the pyridine-SO2 complex.
Conformations of the Esters. IV. The Conformations of Carbamates
Authors: Oki Michinori , Nakanishi Hiroshi
Published: July 2006

It has been confirmed from an infrared spectral study of the C=O, N–H, and N–D stretching regions that primary, secondary, and tertiary carbamates take the s-cis and s-trans conformations with respect to the ester group. The nuclear magnetic resonance spectra and the results of dipole-moment studies support this conclusion.
Syntheses and Reactions of 2-Ethylthio- or 2-Phenylthio-2-cycloalkenones
Authors: Mukaiyama Teruaki , Adachi Takeshi , Kumamoto Takanobu
Published: July 2006

2-Ethylthio- or 2-phenylthio-2-cycloalkenones (five-, six-, or seven-membered ring) were obtained in high yields by the reactions of alicyclic β-ketosulfonium salts with sulfenamides. It was found that dihydrofuran derivatives were obtained in good yields from the sulfonium salts of the cycloalkenones and active methylene compounds.
A Dianthr[14]annulene
Authors: Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

1,2,3,4,5:8,9,10,11,12-Di(1′,8′-anthr)[14]annulene (III) has been synthesized by the Wittig reaction of 1,8-diformylanthracene (IV) and the bis-ylide (VIII) derived from 1,8-bis(bromomethyl)anthracene (VI).
The Reduction of gem-Dibromocyclopropanes by Means of Chromium(II) Acetate or Potassium Pentacyanocobaltate
Authors: Shirafuji Tamio , Oshima Koichiro , Yamamoto Yasusi , Nozaki Hitosi
Published: July 2006

The reduction of gem-dibromocyclopropane(I) with CrII acetate in DMSO gives monobromocyclopropanes (II and III) exclusively, whereas the same components in aq DMF afford cyclopropyl acetates(IV and V) as the major products in addition to II and III. A similar substitution on cyclopropane carbon is observed in the reduction of I with K3Co(CN)5 in DMSO, furnishing cyclopropyl cyanides (IX and X) mainly. The stereochemistry of II, III, IV, and V is determined by the NMR coupling constants and chemical shifts, and that of IX and X, by transformation to the corresponding cyclopropyl methyl ketones derived from cyclopropanecarboxylic acids of known configurations. The reaction of II or III with K3Co(CN)5 is also described.
The Structure of Petasitolone, a New Constituent of Petasites japonicus Maxim
Authors: Naya Keizo , Yoshimura Fumio , Takagi Ichiro
Published: July 2006

Petasitolone(I), a new sesquiterpene isolated from Petasites japonicus Maxim, has been shown to be 8-oxo-11-hydroxy-Δ6(7)-eremophilene by a physico-chemical method, and synthesized from the known fukinone(VI).
An ESR Study of NO2 Adsorbed on Silica Gel Surfaces
Authors: Iwaizumi Masamoto , Kubota Shozo , Isobe Taro
Published: July 2006

NO2 adsorbed on silica-gel surfaces shows temperature-dependent ESR spectra, which can be explained by assuming a restricted rotation of the NO2 molecule, where the preferred axis is the O–O direction. It is concluded from this observation that a hydrogen-bond force between the oxygen of NO2 and OH groups on the silica-gel surfaces plays a part in the NO2-silica-gel interaction. It is also estimated, from the observed hyperfme tensor, that the ONO angle may become slightly smaller when NO2 is adsorbed onto the silica-gel surface from the gas phase.
The Catalytic Activity and Selectivity of Acidic Metal Salt Catalysts for n-Butene Isomerization
Authors: Misono Makoto , Yoneda Yukio
Published: July 2006

Double-bond isomerization of n-butenes over several supported acidic metal salts such as metal sulfates, perchlorates and phosphates including free acids has been investigated at 60°C with the butene pressure of 14 cmHg. The activity and the selectivity of cis-trans isomerization over double-bond migration increased monotonously, as the acid strength of catalysts increased. Acid strength, activity and selectivity of metal salt catalysts increased with the electronegativity of metal ion where free acids were the most strongly acidic and active catalysts (H+>Al3+>Ni2+>Mg2+>Na+), and for a given metal ion they increased with the acid strength of the conjugated acid (ClO4−>SO42−PO43−CH3COO−). The activity and selectivity were explained on the basis of a sec-hutyl carbonium ion mechanism which appears more concerted over weak acids. The active sites for the reaction were suggested to be protonic acid sites closely connected to acid radical.
Acidity Constants of Phenanthrylamines in the Ground, Excited Singlet, and Triplet States
Authors: Tsutsumi Kinzo , Aoki Kazuko , Shizuka Haruo , Morita Toshifumi
Published: July 2006

Measurements of the acidity constants in the ground (pKa(S0)), the lowest excited singlet (pKa(S1)), and triplet states (pKa(T1)) for 2-, 3-, 4-, and 9-phenanthrylamines have been carried out by spectrophotometry. The pKa values obtained were in the order of pKa(S0)>pKa(T1)>pKa(S1). The absorption and emission spectra of the phenanthrylamines were compared with the results of the calculations by means of the semi-empirical SCF-MO-CI method. A linear relationship between the pKa values and the net charge (or charge densities) in the ground and excited states was obtained both experimentally and theoretically.
Adsorption and Decomposition of Formic Acid Adsorbed on Pyrolyzed Polyacrylonitrile
Authors: Kubokawa Yutaka , Miyata Hisashi , Uegaki Yoshihiko
Published: July 2006

Infrared spectra of various pyrolyzed polyacrylonitrile and of deuterated formic acids (HCOOD, DCOOH, and DCOOD) adsorbed on it were investigated. The effect of pyrolysis temperature upon the decomposition products of formic acid adsorbed on the polymer was studied. It was found that parallelism exists between the concentration of the conjugated nitrile group and the percentage of the decomposition of formic acid adsorbed, leading to the conclusion that the active sites for the decomposition reaction are associated with the conjugated nitrile group in the case of polyacrylonitrile pyrolyzed below 300°C. On the other hand, there was a close correlation between the activity for decomposition and the number of free spins in the polymer pyrolyzed above 350°C.
Vibration Spectra and Molecular Structures of n-Butyronitrile, β-Chloropropiononitrile, and β-Bromopropiononitrile
Authors: Fujiyama Tsunetake
Published: July 2006

Infrared and Raman spectra of XCH2CH2CN-type molecules (X=CH3, Cl, and Br) are studied. From the spectral analysis, it is concluded that trans and gauche isomers coexist in the liquid phase, the gauche being more stable. It is also shown that these molecule take gauche configurations in the crystalline phase.
Stability and Extractability of Zinc(II) Thiocyanate Complexes in Several Solvent Extraction Systems
Authors: Moriya Hiromitsu , Sekine Tatsuya
Published: July 2006

The formation and extraction equilibria of zinc(II) complexes with thiocyanate ions have been determined at 25°C. Zinc(II) ions in 1 m sodium perchlorate constant ionic media containing thiocyanate ions at various concentrations have been extracted into chloroform containing β-isopropyltropolone (IPT), into hexane containing trioctylphosphine oxide (TOPO), or into methyl isobutyl ketone (MIBK). The stability constants of the zinc(II) thiocyanate complexes in the aqueous phase were first determined from the decrease in the IPT chelate extraction, and then the distribution constants for the zinc(II) thiocyanate complexes into the latter two solvents were determined. The results were explained by saying that (i) zinc(II) forms the first (logβ1=0.56), second (logβ2=1.32), and the third (logβ3=1.18) complexes in the above aqueous phase, (ii) TOPO in hexane extracts the second complex as an adduct in the Zn(SCN)2(TOPO)2 form, (iii) MIBK extracts both the second and the third complexes, and (iv) the addition of sodium perchlorate causes a salting-in effect in the lower-ligand-concentration region. Some discussion was made of the dissociation of ion-pairs in the organic phase.
Four Radical Species Produced Photochemically in the Solid Mixture of Acridine and Acridan
Authors: Niizuma Shigeya , Kokubun Hiroshi , Koizumi Masao
Published: July 2006

It has been established from measurement of the fusion curve that a 1 : 1 complex of acridine and acridan is formed in the solid state. The complex has an absorption band at 400–500 nm and is considered to be of C-T character although hydrogen bonding plays a role in complexing. Excitation of this complex gives rise to four radical species which display the corresponding characteristic ESR signals a, b, c, and d. The line width of a (α) and the line separations of b, c, d (β, γ, δ) are α=18.0±3.5, β=112±2, γ=137±5, δ=212±6 gauss. Studies on the dependence of the relative intensities of a, b, c, and d upon the acridine-acridan ratio and upon the length of irradiation have led to the conclusion that a and b are due to C- and N-radicals (the latter, triplet with separation of 44 gauss) and c and d are two kinds of radical pair. Detection of ΔM=±2 transition at 1670 gauss (with 9337.4 MHz) also confirmed the above assignment of c and d. It is likely that the mutual transformation occurs only during irradiation. It is concluded that C-radical is more stable than N-radical in agreement with the result in fluid state. An interesting decay feature of signal a was found and was given a plausible interpretation.
Electron-Transfer Reactions of Multidentate-ligand Cobalt(III) Complexes. III. The Reductions of Several Chloro- and Bromo(nitrilopolycarboxylato)cobaltate(III) Ions by Iron(II)
Authors: Kurimura Yoshimi , Meguro Ikuko , Ohashi Kousaburo
Published: July 2006

The reductions of chloro- and bromo(ethylenediaminetriacetatoacetic acid)cobaltate(III), chloro- and bromo (N-hydroxy ethy lethy lenediamine-N,N′, N′-triacetato)cobaltate (III), and dichloro(ethylenediaminediacetato) cobaltate(III) ions by iron(II) in perchloric acid solutions obey the second-order rate expression: –d-[Co(III)]/dt=kc[Co(III)][Fe2+]. The second-order rate constants, kc, and activation parameters for these reactions were determined spectrophotometrically. For the cases of all the Co(III) complexes investigated, an increase in the rate constant with the hydrogen-ion concentration at a constant ionic strength is expressed by: logkc=logk0+A[H+], where k0 and A are constants for the given complex at a constant ionic strength and temperature. The hydrogen-ion dependence can be explained by the difference in the degree of stabilization of the Co(III) anion between that by hydrogen ions and that by sodium ions.
Spectroscopic Studies of Polynuclear Complexes. III. Characteristics of Some μ-Peroxoammine Cobalt(III) Complexes.
Authors: Sasaki Yoichi , Fujita Junnosuke , Saito Kazuo
Published: July 2006

The spectroscopic and chemical properties of various μ-peroxo and μ-superoxo cobalt(III) complexes containing several kinds of polyamine including optically active l-propylenediamine (l-pn) have been studied. The single bridged μ-peroxo complexes have strong absorption peaks at ca. 300 nm, whereas the double-bridged μ-peroxo-μ-amido and μ-peroxo-μ-hydroxo complexes have peaks at ca. 350 nm. The μ-superoxo complexes have two absorption peaks in the visible region at ca. 700 and 480 nm. The former is remarkably stronger for singlebridged species, but both are of almost equal strength for double bridged species. The complexes [LNH3Co(μ-O2(2−))CoNH3L]4+ (L; 2en (ethylenediamine), 2l-pn, and trien(triethylenetetramine)) are spontaneously converted into [LCo(μ-O2(2−), OH)CoL]3+ in water at room temperature. The en ligands in [(dien)(en)Co(μO2(2−))Co(en)(dien)]4+ (dien; diethylenetriamine) are replaced by l-pn in a few days in aqueous solutions containing an excess of l-pn. The absolute configuration of [(l-pn)2Co(μ-O2(2−), OH) Co(l-pn)2]3+ is assigned to be ΔΔ on the basis of circular dichroism spectrum.
Syntheses of (3S, 4R, 15S)-4,15-Dimethyl-1,5-dioxa-3-(3′-formamidosalicylamido)-cyclopentadecane-2,6-dione and Its (15R)-Epimer, New Antimycin Analogs
Authors: Kinoshita Mitsuhiro , Ishii Keitaro , Umezawa Sumio
Published: July 2006

A new type of antimycin analogs, (3S, 4R, 15S)-4,15-dimethyl-l,5-dioxa-3-(3′-formamidosalicylamido)-cyclopentadecane-2,6-dione (10a) and its (15R)-epimer (10b) have been synthesized. The epimeric fifteenmembered amino-dilactone moieties in 10a and 10b were synthesized from a masked l-threonine and t-butyl Dl-10-hydroxyundecanoate. Each of the separated epimeric amino-dilactones was N-acylated with O-benzyl-3-nitrosalicylic acid N-hydroxysuccinimide ester. Hydrogenation followed by N-formylation afforded the anti-fungal substances,10a and 10b. The 10-C-configurations of 10a and 10b were determined as “S” and “R”, respectively. The (15S)-epimer (10a) showed apparently stronger antifungal activity against Piricularia oryzae than that of the (15R)-epimer (10b).
The Reaction of Nitriles under High Pressure, I. The Formation of Triphenyl-1,3,5-triazine via the Equilibrium among Benzonitrile, Alcohols, and Benziminoethers
Authors: Kurabayashi Masahiro , Yanagiya Koshin , Yasumoto Masahiko
Published: July 2006

Benziminoethers were formed from benzonitrile and alcohols to the equilibrium extent, and then 3 mol of benziminoethers were reacted with each other to afford triphenyl-1,3,5-triazine at 2–10kbar and 100–120°C. The equilibrium shifted toward benziminoether with an increase in the pressure. The equilibrium constant decreased progressively in the order of methanol>ethanol≈n-propanol≈n-butanol>isopropanol≈sec-butanol, which accords with the increasing number of substituents on the α-position of the alcohols. The formation of triphenyl-1,3,5-triazine obeyed the second-order reaction mechanism and was also retarded in the same order. The reaction was found to proceed in the following manner: Benziminoethers produced by the addition of alcohols to benzonitrile dimerize through a rate-determining step and then trimerized into triphenyl-1,3,5-triazine. The apparent activation volume of the formation of triphenyl-1,3,5-triazine amounted to −31 cm3 mol−1 at 110°C when methanol was used as the alcohol. The accelerating effect of the pressure on the formation of triphenyl-1,3,5-triazine is concluded to be mainly caused by the shift of equilibrium toward benziminoether. Three isomers of cyanopyridine were converted in good yields into the corresponding triazines under high pressure.
The Preparation of 9-Ethynylanthracene and 9-Ethynyltriptycene and Their Oxidative Coupling
Authors: Akiyama Shuzo , Ogura Fumio , Nakagawa Masazumi
Published: July 2006

The formation of 9,10-dichloroanthracene by reaction of 9-acetylanthracene with phosphorus pentachloride is described. 9-Ethynylanthracene and 9-ethynyltriptycene have been prepared according to Köbrich’s method. The resulting ethynyl compounds have been converted to the corresponding di-ynes using the Eglinton’s oxidative coupling reaction.
Charge Migration through Sigma Bonds in a Fragment Ion from 5,5′-Divaleryl-2,2′-spirobiindan under Electron Impact
Authors: Tatematsu Akira , Naga Shinobu , Sakurai Hiroshi , Goto Toshio , Nakata Hisao
Published: July 2006

In order to examine the nature of charge and radical electron migration in mass spectral fragment ions, 5,5′-di-n-valeryl-2,2′-spirobiindan (3) was prepared and its mass spectrum was measured. The successive loss of two propylene molecules from the molecular ion to give peaks at m⁄e 346 (b) and 304 (c) was clearly indicated by observing appropriate metastable ion peaks. As the radical electron is one of the prerequisites for these fragmentations to occur, the results demonstrate that the charge and radical electron can migrate through sigma bonds in fragment ion b, since the two n-valerophenyl groups cannot be brought into close proximity even with C–C bond fission of the spiro ring. While the strongest peak at m⁄e 331 (a) is ascribable to the ordinary α-fission of the carbonyl group in 3, a moderately intense peak at m⁄e 289 (d) can adequately be explicable by the similar α-fission of the carbonyl group in ion b, the process of which again involves radical electron migration prior to fragmentation.
ESR and Optical Studies on the EDA Complexes of Di-t-butyl-N-oxide Radical
Authors: Murata Yoshifumi , Mataga Noboru
Published: July 2006

It has been confirmed that di-t-butyl-N-oxide (DTBNO) forms EDA complexes with various electron acceptors, and the resulting complexes show CT (charge transfer) absorption bands. Wave-numbers of the CT bands agreed satisfactorily with theory. Charge distributions in the EDA complexes of DTBNO, including hydrogen bonded complexes with proton donors, have been investigated by means of ESR. From the effect of the EDA complex formation upon the hyperfine coupling constant of 14N of DTBNO, contribution of electrostatic forces to complex formation has been demonstrated. However, in the case of complexes with strong acceptors such as tetracyanoethylene, the values of the hyperfine coupling constant have indicated a significant contribution of CT interaction to complex formation.
Molecular Structure of Diacetylene as Studied by Gas Electron Diffraction
Authors: Tanimoto Mitsutoshi , Kuchitsu Kozo , Morino Yonezo
Published: July 2006

The molecular structure of diacetylene has been studied by gas electron diffraction. Thermal-average bond distances are determined to be: rg(C–C)=1.3837±0.0019 Å, rg(C≡C)=1.2176±0.0014 Å, and rg(C–H)=1.0935±0.010 Å. The C–C single bond is about 0.007 Å shorter than that in cyanogen, while the C≡C triple bond is about 0.005 Å longer than that in acetylene. The observed mean amplitudes are slightly larger than the parallel amplitudes based on harmonic calculations. A suggestion has been made to account for the discrepancies by the use of empirical constants representing the interaction between bending and bond-stretching vibrations, which makes the bond distances slightly longer, on the average, in a momentary bent structure than in a linear structure. This interaction also seems to account for a slight difference between the rotational constant B0 estimated from the above rg distances and those derived from spectroscopic experiments.
N-Benzenesulphonyl β-Alanine as a Masking Agent for Hg(II)
Authors: Ghosh Nripendra Nath , Bhattacharyya Anjali
Published: July 2006

N-Benzenesulphonyl glycine and N-benzenesulphonyl α-alanine form water soluble complexes with Hg(II), Cu(II), and Ag(I). But N-benzenesulphonyl β-alanine (RbβH2) gives only stable complex ion Hg(Rbβ)22−, showing that RbβH2 is a highly selective masking agent for Hg(II). Utilising this masking property, methods for detection and determination of Hg(II) have been developed. RbβH2 reacts with Hg(II) at pH≈8, yielding the ion Hg(Rbβ)22− and on subsequent treatment with KI, two equivalents of alkali are liberated. On titrating the alkali liberated with a standard acid, the amount of Hg(II) may be calculated. Interferences due to diverse ions have been studied; Br− and I− interfere. The spot test of Hg(II) based on the same principle has been developed and it appears to be specific under specified condition. The limit of identification is 0.5 μg with a dilution limit of 1:100000.
The Characterization of CdFe(CO)4 and HgFe(CO)4 by Infrared and Mössbauer Spectroscopy and X-Ray Diffractometry
Authors: Takano Tetsuo , Sasaki Yukiyoshi
Published: July 2006

Two compounds, MFe(CO)4 (M=Cd or Hg), were investigated by the use of infrared and Mössbauer spectroscopy and X-ray diffractometry. The infrared data suggested that the M atoms link Fe(CO)4 units to form infinite zig-zag chains; these metal atoms are attached to the iron atom at cis-positions and form an octahedron with four carbonyl groups. The Mössbauer spectra and infrared data indicate that the Cd–Fe and Hg–Fe bonds are not ionic but covalent, that they are as strong as C–Fe bonds in iron carbonyls. The isomorphism of the two compounds was confirmed by the X-ray diffractometry.
The Syntheses and Properties of Some 2,4-Dimethyl-1,5-benzodiazepinium Halogenometalates
Authors: Ouchi Akira , Takeuchi Toshio , Nakatani Mitsuhisa , Takahashi Yoshiaki
Published: July 2006

When 2,4-dimethyl-1,5-benzodiazepinium halide was reacted with a metal halide in ethanolic media, crystalline products, M(C11H13N2)xXy (where X=Br, Cl; M=Co(II), Mn(II), Zn(II), Cd(II), Sb(III) (chloride), Cu(II) (chloride), and Cu(I) (bromide)), were obtained. They are all new compounds. Their electronic and infrared spectra resemble those of the sarting chloride or bromide. The infrared band at about 1639 cm−1 of the chloride shifts to the lower-wave-number side when it is turned into a halogenometalate. On the other hand, the characteristic ν(M–X) bands were found in the far-infrared spectra of the halogenometalates, These compounds are likely to be ionic compounds consisting of the halogenometalato anion and the 2,4-dimethyl-1,5-benzodiazepinium cation.
The Dehydration of N-Benzyloxy and N-Hydroxymaleamic Acid and the Isomerization of N-Benzyloxyisomaleimide
Authors: Narita Mitsuaki , Akiyama Masayasu , Okawara Makoto
Published: July 2006

The dehydration of N-benzyloxy and N-hydroxymaleamic acids and the isomerization of N-benzyloxyisomaleimide were carried out under various conditions to obtain N-benzyloxyisomaleimide, N-hydroxyisomaleimide, and N-benzyloxymaleimide. N-substituents, such as benzyloxy, hydroxy, and acetoxy groups, depress the reactivity of nitrogen electronically and facilitate the formation of isomaleimides in the dehydration of N-substituted maleamic acids. The thermal isomerization of N-benzyloxyisomaleimide to the maleimide has been successful only in N,N-dimethylformamide. Further the conversion of isomaleimide to maleimide was performed via the addition of hydrogen bromide to isomaleimide followed by isomerization and dehydrobromination.
The Mechanism of Silver Perchlorate Catalyzed Solvolysis Reaction of 2-Chlorocyclohexanone-1-14C
Authors: Masuike Taketoshi , Furukawa Naomichi , Oae Shigeru
Published: July 2006

Silver perchlorate assisted solvolysis of 2-chlorocyclohexanone-1-14C in ethanol-water solution gives 2-ethoxycyclohexanone-x-14C. Successive degradation of the product reveals that the 14C activity is distributed in both the carbonyl carbon and the α-carbon of ethoxyketone. The 14C distribution pattern suggests that a part of the reaction proceeds via an epoxide intermediate which is formed by the initial attack of ethanol on the carbonyl carbon, followed by the migration of carbonyl oxygen to the α-carbon of 2-chlorocyclohexanone.
Tracer Study of the Reactions of Diphenyl Sulfone and Diphenyl Sulfoxide with Diphenyl Disulfide
Authors: Oae Shigeru , Tsuchida Yoshiyuki , Nakai Mamoru
Published: July 2006

Diphenyl sulfoxide and diphenyl sulfone were found to react with diphenyl disulfide at elevated temperatures, forming in both reactions diphenyl sulfide and sulfur dioxide. On the basis of 35S and 14C tracer experiments, these reactions were found to proceed through quite different mechanistic routes, viz., S–O bond fission in the case of sulfoxide and C–S bond fission in sulfone. The reactions apparently proceed through the attack of the thiyl radical on the sulfoxide and sulfone functions. Further mechanistic details of the reactions are discussed.
Studies of Phosphorylation. V. The Synthesis of Inosine-5′-thiophosphates
Authors: Haga Kazuko , Kainosho Masatsune , Yoshikawa Masaharu
Published: July 2006

Two isomers of inosine-5′-thiophosphates, inosine-5′-phosphorothionate and 5′-deoxy-5′-thioinosine-5′-phosphorothioate, were synthesized by the direct phosphorylation of inosine with phosphorus thiochloride, and by the treatment of 5′-deoxy-5′-iodoinosine with trisodium phosphorothioate, respectively. The structure of the thiophosphate residues was identified by means of 31P NMR. The flavoring activities of these thiophosphates were measured as the synergistic strength with monosodium glutamate; it was found that the strength of each compound was lower than that of inosine-5′-phosphate.
Studies on Microbial Utilization of Petroleum. I. Separation and Characterization of Carotenoids Produced by a Species of Brevibacterium in Hydrocarbon Media
Authors: Sakurai Hyoichiro , Kato Kenji , Sakai Toshio , Masuda Yoshiro , Kuriyama Tohoru
Published: July 2006

Ten pigment fractions were separated from a Brevibacterium sp. KY-4313 in hydrocarbon fermentation. The pigments were extracted from cell with a mixture of petroleum ether and acetone, and purified by column and thin-layer chromatography. The principal carotenoid of this organism was identified as canthaxanthin (4,4′-dioxo-β-carotene) by using visible, IR, NMR, and mass spectra of the pigment. Three other pigments were characterized as β-carotene, echinenone (4-oxo-β-carotene), and 15-cis-4,4′-dioxo-β-carotene. Three carboxylic carotenoids and three other carotenoids were also separated but their structures were left unidentified. Quantitation of the pigments showed that canthaxanthin represented 53% and its cis-isomer 20% of the pigments separated from extracts. β-Carotene derivatives comprise more than 80% of the pigments. Canthaxanthin and echinenone have not previously been reported as bacterial pigments in hydrocarbon fermentation.
The Infrared Spectra of Metallooctaethylporphyrins
Authors: Ogoshi Hisanobu , Masai Naruhito , Yoshida Zen-ichi , Takemoto James , Nakamoto Kazuo
Published: July 2006

The infrared spectra of the Mg(II), Co(II), Cu(II), Zn(II), Pd(II), Ni(II), and Ge(IV)Cl2 complexes of octaethylporphyrins have been studied over the range 4000–100 cm−1. Metal sensitive bands have been observed at about 980, 920, 340, 230, and 130 cm−1.
Studies of Compounds Related to Azines. VII. The Pyrorlysis of 2-Acetylthiophene- and 2-Acetylfuranketazine
Authors: Tsuge Otohiko , Watanabe Haruyuki , Hokama Kozo
Published: July 2006

As part of a study attempting to elucidate the relation between the chemical structure of an azine and its pyrolysate, the pyrolyses of 2-acetylthiophene- (I) and 2-acetylfuranketazine (II) have been investigated. The pyrolysis of I at 270°C afforded principally nitrogen, ammonia, and 7-methy 1-5-(2-thienyl)-thieno[2,3-c]pyridine (III), plus lesser quantities of thiophenecarbonitrile and 2-acetylthiophene. The reductive desulfurization of III, followed by oxidation, afforded pyridine 2,4,6-tricarboxylic acid via 5-n-butyl-7-methyl-thieno[2,3-c]pyridine and 2-n-butyl-4-ethyl-6-methylpyridine. On the other hand, II was pyrolyzed to give nitrogen, ammonia, and tars as the major products, together with furan, furancarbonitrile, 2-acetylfuran, 5-(2-furyl)-7-methyl-furo[2,3-c]pyridine, and 2,4,6-tri(2-furyl)pyridine.
Stoichiometric Carbonylation of Aryl Halide with Nickel Tetracarbonyl in the Presence of Potassium Acetate
Authors: Nakayama Mikitake , Mizoroki Tsutomu
Published: July 2006

In the stoichiometric reaction of aryl halide with Ni(CO)4 in methanol to form the corresponding ester, it has been found that the carbonylation is effectively promoted by adding potassium acetate to the starting materials, and that four moles of the ester are obtained from one mole of Ni(CO)4 without any appreciable side reactions. From the inhibition by gaseous carbon monoxide and the IR measurements during the carbonylation, it has been concluded that nickel tricarbonyl, Ni(CO)3, is the initiator of the carbonylation and that its regeneration is the rate-determining step. The present results provide a basis on which the course of the carbonylation of aryl halide with carbon monoxide catalyzed by Ni(CO)4 under high temperatures and pressures may be reasonable explained.
Polarography of Halides in Dimethylformamide. VI. The Formation of the Benzhydryl Radical from Benzhydryl Bromide and Its Subsequent Reduction at the Dropping Mercury Electrode
Authors: Matsui Yoshihisa , Soga Takashi , Date Yoshio
Published: July 2006

The polarographic behavior of benzhydryl bromide at the dropping mercury electrode was investigated in dimethylformamide at 25degC. It gives three waves, with half-wave potentials at about +0.19, −0.15, and −1.00 V vs. SCE. The first wave is anodic, while the others are cathodic. It was concluded that benzhydryl bromide, prior to being electrolytically reduced, rapidly reacts with the mercury of the cathode according to the following equation:

3(C6H5)2CHBr+Hg→2(C6H5)2CH·+(C6H5)2CH++HgBr3−

The first wave given by the bromide was ascribed to the oxidation of HgBr3− to HgBr2; the second, to the reduction of HgBr3− to Hg and Br−, and the third, to the reduction of (C6H5)2CH· to (C6H5)2CH−. The cation, (C6H5)2CH+, was found to give no wave. Such behavior of benzhydryl bromide was discussed in comparison with that of the corresponding chloride, which gives a single wave with a usual two-electron transfer.
The Mechanism of the Reaction of Quinolines with Organolithium Compounds
Authors: Otsuji Yoshio , Yutani Kiyihiko , Imota Eigi
Published: July 2006

The treatment of lepidine (IV) with phenyllithium in ether afforded 2-phenyl-4-methylquinoline (V) along with small amounts of 2-phenylquinoline (VI) and 2-methyl-4-phenylquinoline (VII). The similar treatment of IV with phenyllithium and then with ethyl chloroformate gave 1-ethoxycarbonyl-4-methyl-4-phenyl-1,4-dihydroquinoline (VIIIa). The alkaline hydrolysis of VIIIa produced a mixture of V, VI, and VII. Similar experiments were carried out on the reactions between IV and n-butyllithium and between quinoline and phenyllithium. On the basis of these results and other observations, a new mechanism involving an addition-rearrangement-elimination was proposed for the reaction of quinolines with organolithium compounds.
The Cationic Polymerization of Methallyl Vinyl Ether
Authors: Yuki Heimei , Hatada Koichi , Emura Tomoyuki , Nagata Kazuhiko
Published: July 2006

The polymerization of methallyl vinyl ether was carried out in toluene by means of BF3·OEt2. The reaction proceeded through the vinyl double bond, giving a polymer containing one methallyl double bond per monomeric unit. The polymer obtained below −78°C was a white powder and had an isotactic configuration. The molecular weight of the polymer decreased with an increase in the polymerization temperature, and the polymer obtained at 0°C was a viscous liquid. In n-heptane, the yields of the polymer decreased and a part of the polymer obtained was insoluble in usual organic solvents, probably because of the cross-linking which occurred during the polymerization reaction. In n-heptane-toluene mixtures, the yields were much higher than those in toluene or n-heptane alone. The NMR spectra of the polymer were measured in CCl4, benzene, pyridine, and quinoline at various temperatures in order to investigate the polymer-solvent interaction; the π-complex formation between the monomeric unit of the polymer and the aromatic solvent molecule was suggested.
4-Acetylierung der 5-Hydroxy-indol-Derivate
Authors: Suehiro Tadashi , Niitsu Machiko
Published: July 2006

5-Hydroxy-4-acetyl-2-äthoxycarbonyl-indol und 5-Hydroxy-2-methyl-4-acetyl-indol wurden durch die Friedel-Crafts-Acetylierung oder durch die Fries-Umlagerung in Gegenwart von Lewis-Säure bzw. unter Belichtung hergestellt. Die Acetylierung wird stark von dem sterischen Faktor des 3-Subtituenten beeinflusst und bei 5-Hydroxy-2-methyl-3-äthoxycarbonyl-indol läuft die 6-Acetylierung ab. Wenn kein 3-Substituent vorhanden ist, wird es eher an der 4-Stellung als an der 6-Stellung acyliert. Der Strukturbeweis wurde aus den NMR-Spektren geführt. 5-Hydroxy-4-acetyl-2-äthoxycarbonyl-indol lässt sich in Dimethylformamid durch Natriumhydrid und Alkylhalogenid an den O- und N-Stellungen alkylieren.
The Chemisorption of Nitric Oxide and Nitrogen on Rhenium
Authors: Tamura Teijiro
Published: July 2006

The chemisorption of nitric oxide and nitrogen on a polycrystalline rhenium filament was studied using flash-desorption mass spectroscopy. For the chemisorption of nitric oxide, the initial sticking probability was found to be close to unity, with a saturation coverage of 5.2×1014 molecules/cm2 at room temperature. Nitric oxide adsorbs nondissociatively, and dissociation occurs at an elevated temperature. The rate of the desorption of nitrogen from the nitric oxide layer is roughly proportional to θ2. The majority of the oxygen in the nitric oxide layer was presumed to be liberated as rhenium oxide. The nitrogen adsorption was investigated in order to compare it with the nitric oxide adsorption. The saturation coverage and the initial sticking probability were 1.08×1014 molecules/cm2 and 0.003 respectively.
Inter and Intramolecular Charge and Excitation Transfer Observed in Irradiated Polyvinyl Chloride Particles with Surface-coated Additives
Authors: Ueda Hisashi , Yashiro Dairokuro
Published: July 2006

Particles of polyvinyl chloride were coated with small amounts of various aromatic compounds from benzene solutions and were then irradiated in a vaccum. The ESR spectra of the specimen thus obtained were recorded. Though the amount of the coated additives, in the ratio of 1 molecule for 100 monomer units of PVC, was small, strong effects on the ESR spectra were observed. The additives coated on the surface affect the ESR spectra in two ways. They cause a decrease in the total ESR absorption intensity; this was observed with all the additives studied. They also often transform the ESR spectrum; this was observed with several additive compounds, such as p-benzoquinone, tetramethylphenylenediamine-2·HCl, chrysene, hydroquinone, nitrosonaphthol, perylene, and diphenylpicrylhydrazine. Only the conduction of the excitations, holes and electrons formed in the bulk particles, to the surface of the particle can explain these results. On the surface of the particle, the excitation or the electric charge is transferred to the additive by means of an intermolecular interaction with it. The possibilities for the mechanism of the conduction of the excitation and the electric charges, and the ionization processes are discussed.
The Electrodeposition of Aluminum from a Solution of Aluminum Bromide in N,N-Dimethyl Aniline
Authors: Hisano Takeo , Terazawa Toshio , Takeuchi Ichiro , Inohara Shinzo , Ikeda Hiroshi
Published: July 2006

This paper will describe that metallic aluminum was deposited electrolytically from a solution of aluminum bromide in dimethyl aniline with a current efficiency of 95% or more under optimum conditions. The superposition of a sinusoidal alternating current (AC) on the electrolysis direct current (DC) affected the properties of coatings and the throwing power of solutions to a great extent. A smooth, white-bright, ductile, and adherent coating was obtained under such appropriate conditions as that the frequency of AC was 60 Hz, the AC to DC ratio of 2 to 3. Aluminum dissolved anodically, and it was deposited at the cathode. The freezing temperature-composition diagram indicated the occurrence of two stoichiometric molecular complexes, AlBr3·C6H5N(CH3)2 and AlBr3·2C6H5N(CH3)2, and the former was isolated.
Electronic Structure of Lone Pairs. II. Disulfides and Acyl Thiol
Authors: Yamabe Hiroko , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The electronic structure and the electronic transition of three cyclic disulfides, (CH2)3S2, (CH2)4S2, and (CH3)2S2, are calculated by the semi-empirical ASMO SCF method in order to study the interaction of the neighbouring lone pairs of the S–S bond in connection with the ability of reductive scission. It is concluded that the absorption at 2500–3000 Å is the transition of n–σ* and that the variation in the maximum for the various cyclic disulfides and the chain disulfide are induced by the change in the dihedral angle that a molecule can take. The electronic structure and the reactivity of (CH3)2S2, CH3SSH, and CH3SCOCH3 are then discussed on the basis of an extended Hückel calculation. It is suggested that there is the possibility of an interaction between two molecules, R2S2, through the S–S bond of each molecule, in the HO of one molecule and in the LV of another.
The Optical Activity of Bis-1,1′-spiroindanes. The Direct Calculation of Optical Rotational Strengths
Authors: Hagishita Sanji , Kuriyama Kaoru
Published: July 2006

A calculation based on Longuet-Higgins and Murrell’s method using the MO’s of aniline and phenol obtained by the SCF-MO-CI calculation is carried out for the π-electron structures of (−)-6,6′-diamino-(I) and (−)-6,6′-dihydroxy-bis-1,1′-spiroindane (II). These wave functions are then used to calculate the rotation strengths of these compounds. The circular dichroism curves calculated from the results, assuming a Gaussian curve, are compared with the observed spectra; a quantitative agreement with the experimental value is found. The nature of the transitions and the origin of the optical activity are also discussed.
The Cation Radical Salts of Phenothiazine and Related Compounds
Authors: Iida Yôichi
Published: July 2006

The cation radical salts of phenothiazine bromide, phenothiazine bisulfate monohydrate, and phenothiazine picrate were prepared. The absorption spectra in a dilute hydrochloric acid solution and the solid-state spectra of the salts were examined. The solid-state spectra showed a strong charge-transfer band and blue-shifts of the high-energy bands, unlike the absorption spectra in solution. The magnetic susceptibilities of these salts were measured at room temperature. They were found to be diamagnetic, with values almost corresponding to those of the diamagnetic contribution of the salts, except for that of the picrate. These spectroscopic and magnetic properties were discussed on the basis of the charge-transfer interaction between the phenothiazine cation radicals. The properties of the usual phenothiazine-picric acid charge-transfer complex and the holoquinoid phenothiazine perchlorate were investigated in association with those of the cation radical salts.
Studies of the Formation Mechanism of Sodium Tripolyphosphate from Orthophosphates by the Use of Radioisotopes
Authors: Iida Takaya , Takai Nobuharu , Yamabe Takeo
Published: July 2006

The reaction process of an equimolar mixture of mono- and disodium orthophosphates was examined to serve as a reference for the considerations of the mechanism of the formation of sodium tripolyphosphate. Differential thermoanalysis, thermogravimetric analysis, X-ray diffraction analysis and thin-layer chromatographic analysis were done. Particularly, the reaction mechanisms (the formation of liquid Na3HP2O7, etc.) were also examined by the use of the “32P” radioisotope. The reaction process is as follows:

(Remark: Graphics omitted.)

A feedback phenomenon of Na2H2P2O7 was observed.