bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies of the Alkaline Earth Complexes in Various Solutions. VI. The Extraction and Complex Formation of Beryllium(II) in Sodium Perchlorate Media Containing Some Univalent Inorganic Anions
Authors: Serine Tatsuya , Komatsu Y\={u} , Sakairi Mitsuo
Published: July 2006

The distribution of beryllium(II) between methylisobutylketone containing TTA (thenoyltrifluoroacetone) and aqueous 4.0 m sodium perchlorate constant ionic media has been measured by using a carrier-free beryllium-7 tracer. The distribution behavior, determined as a function of the TTA and the hydrogen ion concentration, was explained in terms of the extraction of the Be(TTA)2, the Be(ClO4)2 and the mixed species Be(TTA)-(ClO4), and their extraction constants were determined. Then, the stability constants for the chloride, bromide, and nitrate complexes were determined from the decrease in the TTA extraction when some of the perchlorate ions in the aqueous phase were replaced by the ligand anions. Those of the thiocyanate complexes, on the other hand, were determined from the extraction of Be(SCN)2 species with TBP (tributylphosphate) in hexane. It was concluded that the stabilities of these complexes are very low; the values β1 and β2 range between 1 and 0.1, but still these complexes should be taken into account in any discussion of the chemical behavior under some experimental conditions.
Elimination Reactions Promoted by Fluoride Ion in Acetonitrile. Elimination Reaction from 2-Arylethyl Derivatives
Authors: Hayami Jun-ichi , Ono Noboru , Kaji Aritsune
Published: July 2006

Rates of bimolecular elimination have been determined for the reaction of 2-arylethyl bromides, chlorides, and tosylates with anhydrous tetraethylammonium fluoride in acetonitrile. The rates of elimination reactions in this new base system were much faster than those in conventional base systems (alkoxide-alcohol). The Hammett ρ values were found to be ρ=2.033 (X=Cl) at 25.0°C and ρ=1.879 (X=Br) at 5.0°C for p-Y-C6H4CH2CH2X. Kinetic deuterium isotope effects were determined using 2-phenylethyl-2,2-d2 bromide and chloride to be kH/kD=3.99 (X=Cl) and 5.03 (X=Br). These data and the low kOTs/kBr ratio suggest that fluoride-ionpromoted elimination reaction proceeds through a very tight transition state where β-proton is less than half transferred to the base.
The Hofmann Rearrangement. III. Kinetic Substituent Effects of 4- and 5-Substituted 2-Chloro-N-chlorobenzamides
Authors: Imamoto Tsuneo , Tsuno Yuho , Yukawa Yasuhide
Published: July 2006

The kinetic measurements of the Hofmann rearrangement of 2,4-, 2,5- 2,6-, and 3,5-disubstituted N-chlorobenzamides were carried out. The rate constants of 4- and 5-substituted 2-chloro-N-chlorobenzamides were applicable to the LArSR relationship:

logk⁄k0=−2.21(σ0+0.69Δ\barσR+)+0.003

indicating that the reactivity of the 2-chloro series was subjected to a larger additional conjugation effect than that of the 2-unsubstituted series. The detailed discussion of the reaction mechanism on the basis of these results supported strongly the concerted mechanism.
The Cyclization Products from Acetone with Cyanoacetic Esters
Authors: Igarashi Minoru , Midorikawa Hiroshi
Published: July 2006

The structure of the cyclization product from acetone with the cyanoacetic ester has been established as 3-alkoxycarbonyl(cyano)methylene-6-cyano-5,5-dimethyl-1-cyclohexene-1-ol by means of infrared and NMR spectroscopic determinations and by successive degradations.
Further Studies of the Chemical Cleavage of the Tryptophyl Bond by Ozonization-hydrazine Treatment
Authors: Sakiyama Fumio , Sakai Shin-ichiro
Published: July 2006

The second step (hydrazine treatment) in the chemical cleavage of the tryptophyl bond according to the scheme proposed previously was further studied under mild conditions using a model N′-formylkynurenyl peptide, carbobenzoxy-l-alanyl-N′-formyl-l-kynurenyl-l-leucine. The reaction of the model compound with an excess of hydrazine acetate at 25–30°C for 24–48 hr gave rise to the selective cleavage of the kynurenyl bond together with a concomitant tetrahydropyridazone formation. The maximum cleavage was 80–90%. It was then suggested that the incomplete cleavage of the tryptophyl bond in synthetic oligopeptides by means of ozonizationhydrazine treatment was mainly due to insufficient conversion of the indole nucleus into N′-formylanthranyl grouping in the first step (ozonization).
The Preparation of Deoxyguanosine Oligomers on an Insoluble Polymer Support
Authors: Shimidzu Takeo , Letsinger Robert L
Published: July 2006

The syntheses of deoxyguanosine-containing oligonucleotides, deoxyguanylyldeoxyguanylyldeoxyguanosine (d-GpGpG), deoxyguanylyldeoxyguanylyldeoxyguanylyldeoxyguanosine (d-GpGpGpG) and deoxyguanylyldeoxyguanylyldeoxyguanylylthymidine (d-GpGpGpT) have been described. Those nucleotidic materials were synthetized on an insoluble polymer support; the polymer was a copolymer of styrene, p-vinylbenzoic acid, and divinylbenzene. The blocking group used at the N-position of deoxyguanosine was di-p-methoxytrityl.
Nucleoside Analogs. II. A Synthesis of 9-Adenyl-deoxyinositols
Authors: Suami Tetsuo , Fukai Yasushi , Sakota Yukio , Karimoto Makoto , Takoi Nobuo , Tsukamoto Yoko
Published: July 2006

Four 9-adenyl-deoxyinositols were prepared by a reaction between 4-amino-6-chloro-5-nitropyrimidine (1) and inosamines (2a, 2b, 2c, and 2d), followed by a reduction and a cyclization. In the present article, 1-(6′-amino-9′-purinyl)-1-deoxy-scyllo-inositol (5a), 1-(6′-amino-9′-purinyl)-1-deoxy-muco-inositol (5b), 2-(6′-amino-9′-purinyl)-2-deoxy-epi-inositol (5c), and 2-(6′-amino-9′-purinyl)-2-deoxy-myo-inositol (5d) were described. These compunds exhibited an inhibitory effect against piricularia  oryzae.
The Differential Thermal Analysis of Potassium Oxalate
Authors: Higashiyama Tatsuo , Hasegawa Shigeo
Published: July 2006

From the differential thermal and thermogravimetric analyses of potassium oxalate together with the X-ray diffraction studies, three crystallographic modifications of the anhydrous salt were found. When potassium oxalate monohydrate crystals were dehydrated at, e.g., 140°C, phase II, which is stable below 381°C, appears. The crystal in phase II has an orthorhombic unit cell (a=10.9, b=6.11, and c=3.44 Å at 17°C) and transforms at 381°C into phase I, which is stable above 381°C up to the temperature where the decomposition begins. The crystals in phase I belong to the tetragonal system (a=7.01 and c=7.53 Å at 404°C). The transition between phases II and I is not reversible in an exact sense, and when cooled phase I endures down to 215°C, where it transforms(reversibly) into phase III. Phase III can exist at room temperature. When heated, phase III transforms into phase I at 215°C (often accompanied by a partial transformation to phase II). The resulting phase then transforms into phase II. At all temperatures below 381°C phases I and III are metastable with respect to phase II, and they transform into phase II. The decomposition of potassium oxalate in an oxygen-free atmosphere seems to proceed in two stages.
Dehydration and Dehydrogenation of Alcohols over Acid-Base Bifunctional Catalysts
Authors: Niiyama Hiroo , Echigoya Etsuro
Published: July 2006

Alkaline earth silicates having both acidic and basic sites can be considered as acid-base bifunctional catalysts. Dehydration and dehydrogenation of alcohols over these catalysts were carried out. Correlation between the selectivity and acid-base properties of alcohols and the catalysts was studied. It was found that acid-base properties of both the catalysts and the alcohols were cooperative in determining the selectivity of reaction.
The Electron-acceptor Strengths of Some Substituted Naphthoquinones
Authors: Saito Gunzi , Matsunaga Yoshio
Published: July 2006

The electron-acceptor strengths of the substituted naphthoquinones were compared with that of p-chloranil in terms of their complexing properties. The following electron affinities were estimated: 2.05 eV for 2,3-dichloro-1,4-naphthoquinone, 2.24 eV for 2,3-dichloro-5-nitro-1,4-naphthoquinone, 2.74 eV for 2,3-dicyano-1,4-naphthoquinone, and 2.78 eV for 2,3-dicyano-5-nitro-1,4-naphthoquinone.
Solvolysis of Organic Phosphates. IV. 3-Pyridyl and 8-Quinoly Phosphates as Effected by the Presence of Metal Ions
Authors: Murakami Yukito , Sunamoto Junzo
Published: July 2006

Influence of nickel(II), copper(II), and thorium(IV) ions on the hydrolysis of 3-pyridyl and 8-quinolyl phosphates was investigated at μ=0.10 in a lower pH region. The reaction in the presence of the bivalent metal ions followed apparent first-order kinetics with respect to the phosphates in homogeneous phase. The copper ion showed a positive catalytic effect only on the hydrolysis of 8-quinolyl phosphate, and such effect increased markedly as pH was raised. The nickel ion, however, did not show any significant effect on the hydrolysis of both phosphates. The requisites for effective catalysis of bivalent metals have been postulated previously: (1) preliminary chelate formation, and (2) transitional chelate formation. Accordingly, complex formation of the present phosphates with copper(II) and nickel(II) was studied by means of potentiometric measurements. The results strongly suggest the importance of (1) for yielding catalytic efficiency. The presence of the thorium ion resulted in a profound acceleration of hydrolysis of both phosphates in a relatively lower temperature range. The reaction rate did not follow the simple kinetic law although the reaction system was kept homogeneous under the present experimental conditions. The complex formation with the phosphate moiety, which would provide effective charge neutralization for the substrate, is most likely the necessary cause for the thorium-catalysis. Plausible reaction mechanisms and the corresponding potential energy correlations were postulated for the present catalysis.
The Carbon-catalyzed Oxidation of Co(II)-Ethylenediaminetetraacetate by Molecular Oxygen
Authors: Tomita Akira
Published: July 2006

The kinetics of the oxidation of a cobaltous complex of ethylenediaminetetraacetic acid (EDTA) is determined volumetrically at 50.0°C in the presence of several kinds of carbon as catalysts. One mole of oxygen was used to oxidize four Co(II) ions, and all the Co(II) ions were oxidized to Co(EDTA)− ions quantitatively. The rate of oxygen uptake was found to change from zeroth order to first order with respect to the complex ion during the course of oxidation; it was also found to be first order with the oxygen pressure and the amount of the carbon catalyst. The catalytic activity of the carbon was correlated to the quantity of surface basic oxides of the carbon. A possible mechanism which can account for the above results is proposed.
Restricted Rotation Involving the Tetrahedral Carbon. I. Some Diels-Alder Adducts Derived from 9-Substituted Anthracenes
Authors: Oki Michinori , Suda Minoru
Published: July 2006

9-t-Butylanthracene was treated with dimethyl acetylenedicarboxylate and benzoquinone to give Diels-Alder adducts. The NMR spectra of these adducts suggest that the internal rotation about the C1–CBu bond is not taking place on the NMR time scale. On the other hand, a Diels-Alder adduct prepared from 9-isopropylanthracene and dimethyl acetylenedicarboxylate shows the coalescence phenomenon of the NMR signals when the temperature is raised. The possibility of optical resolution due to hindered rotation about the sp3–sp3 carbon bond is pointed out.
Reactions of Sulfonium and Pyridinium Salts with Alkyl Nitrite
Authors: Mukaiyama Teruaki , Saigo Kazuhiko , Takei Hisashi
Published: July 2006

It was found that α-bromo-α-hydroxyimino compounds were obtained in good yields by the reactions of sulfonium bromides, such as dimethylphenacylsulfonium bromide, acetonyldimethylsulfonium bromide and ethoxycarbonylmethyldimethylsulfonium bromide, with isopropyl nitrite. On the other hand, (α-hydroxyiminophenacyl and -acetonyl)pyridinium bromides were obtained in quantitative yields by the reactions of pyridinium bromides, such as phenacylpyridinium bromide and acetonylpyridinium bromide, with isopropyl nitrite. Further, the reactions of α-bromo-α-hydroxyimino compound or (α-hydroxyiminophenacyl)pyridinium bromide, which were obtained by the above mentioned reactions, with several nucleophiles were studied.
Kinetics and Equilibrium Positions of cis-trans Isomerization of 1,2-Bis(phenylthio)ethylene and Its Exchange with Benzenethiyl Radicals
Authors: Ohno Atsuyoshi , Saito Tomo’o , Kudo Akio , Tsuchihashi Gen-ichi
Published: July 2006

Kinetics of the cis-trans isomerization of 1,2-bis(phenylthio)ethylene induced by benzenethiyl radicals and the exchange of phenylthio group have been studied by using thiophenol-phenyl-14C Pseudo-first order rate constants for the isomerization and the exchange are 2.08±0.22×10−5 sec−1 and 2.03±0.26×10−5 sec−1 at 50°C, respectively. The cis/trans ratio of this olefin is 55–58/45–42 at the completion of the reaction, which differs from the value obtained from the reaction induced by iodine (48–49/51–52). The difference has been interpreted with the idea that the isomer composition in the cis-trans isomerization is determined by kinetic factors when the reaction is initiated by thiyl radicals.
The ESR Spectra of 2- and 6-Methoxyazulene Anion Radicals
Authors: Ikegami Yusaku , Seto Shuichi
Published: July 2006

The electron spin resonance spectra of 2- and 6-methoxyazulene anion radicals have been examined. The radicals were generated from neutral species either by electrolytic reduction in N,N-dimethylformamide or by the reduction with alkali metals in ethereal solvents. The experimental splitting constants are explained satisfactorily in terms of the calculated spin densities by McLachlan’s procedure.
A Theoretical Study of the Electronic Structures of Several Methyl Compounds of Group I, II, and III Elements
Authors: Ohkubo Katsutoshi , Shimada Hidetoshi , Okada Masahide
Published: July 2006

The electronic states of the group I, II, and III methyl compounds were investigated using the extended Hückel method, with particular reference to the nature of the bond of metal-carbon. First, the monomers of the group I methyl compounds indicated remarkable electron-localizations on the carbon atom in CH3. (CH3Li)4 was found to be a possible tetramer, its total energy being lower by 0.34 eV per CH3Li unit than that of the CH3Li-monomer in spite of the unstability of (CH3Li)2. Second, (CH3)4Be2 was more stable than (CH3)2Be by ca. 4.04 eV per (CH3)2Be unit. Third, the stability of (CH3)3B in the form of a monomer was understood well by the fact that its π-bond nature is so much in comparison with that of (CH3)3Al. Finally, the reactivities in a series of the groups were discussed briefly in connection with the electronic states.
Interaction between TCNQ and Surfactant. III. The Effect of Light on the Spectra of TCNQ Solubilized in Surfactant Solutions
Authors: Muto Shinya , Degughi Katsuhiko , Shimazaki Yoshikazu , Aono Yoshiaki , Meguro Kenjiro
Published: July 2006

The absorption spectra of 7,7,8,8-tetracyanoquinodimethane (TCNQ) solubilized in surfactant solutions were found to be influenced by day light (hereafter referred to as light). The formation of the monomer band of TCNQ, anion radical in the aqueous solution of DPCl (dodecylpyridinium chloride), DPBr (dodecylpyridinium bromide) and C12E8 (homogeneous octaethylene glycol dodecylether) were enhanced by light. On the other hand, the spectra of TCNQ solubilized in surfactant micelle in the dark suggested that TCNQ exists as dimer anion radical form (TCNQ)2\ewdot. Thus, in solubilized state of TCNQ in micelle there is an equilibrium between monomer TCNQ\ewdot and dimer (TCNQ)2\ewdot, which seems to be easily influenced by light and surfactant. Appearance of a monomer radical band was remarkable in DPCl, DPBr, and C12E8 but only the dimer band was found in SDS even in the light.
The Coadsorption of Nitric Oxide, Nitrogen, and Oxygen on Rhenium
Authors: Tamura Teijiro
Published: July 2006

The coadsorption of nitric oxide, nitrogen, and oxygen on a polycrystalline rhenium filament was studied using flash desorption mass-spectroscopy. Substitutional desorption was not observed during the adsorption of nitric oxide, nitrogen, or oxygen on preadsorbed leayers. No oxygen or nitrogen adsorbs on rhenium saturated with nitric oxide. However, nitric oxide adsorbs on rhenium saturated with nitrogen or oxygen. The strength of the chemisorption bond between rhenium and adsorbed species becomes weaker in the order of: nitric oxide, oxygen, and nitrogen. When the same amount of nitric oxide molecules exist in various coadsorbed layers, the Tp of the nitrogen desorption spectrum from these layers is shifted to a lower temperature with an increase in the number of oxygen atoms in them, because the strength of the chemisorption bond of Re–N is weakened by the strongly-bonded Re–O. No desorption of the nitric oxide molecule from a coadsorbed layer of the “N2+O2” on rhenium was observed.
The Acylation of bz-Hydroxy- and bz-Methoxy-2,3-dimethylbenzofurans and the Synthesis of Furobenzopyranone Derivatives
Authors: Kawase Yoshiyuki , Yamagughi Seiji , Oki Nobuo , Okumura Fumiko
Published: July 2006

The action of acetic acid, phenylacetic acid, or β-phenylpropionic acid and polyphosphoric acid on 5-, 7-, and 6-hydroxy-2,3-dimethylbenzofurans afforded 6-acyl-5-hydroxy-, 6-acyl-7-hydroxy-, and 5-acyl-6-hydroxybenzofurans, some of which were also obtained by the Friedel-Crafts acylation of the corresponding methoxybenzofurans. The hydroxyketones thus obtained were converted to dimethylfuro derivatives of 4-hydroxycoumarins and isoflavones, and 3-benzyl-4-hydroxyfurocoumarins were also prepared by the thermal condensation of the hydroxybenzofurans and diethyl benzylmalonate.
Tetraaminoethylenes. I. The Preparation and Some Reactions of Tetrapiperidino- and Tetramorpholinoethylene
Authors: Tsuge Otohiko , Yanagi Kiyoshi , Horie Masako
Published: July 2006

The preparation of new tetraaminoethylenes was attempted by the reaction of chlorotrifluoroethylene (CTFE) with several amines. It has been found that CTFE reacted with piperidine and morpholine to give tetrapiperidino- (TPE) and tetramorpholinoethylene (TME) in moderate yields respectively, although no tetraaminoethylenes were formed in the reactions with diethylamine, pyrrolidine, aniline, N-alkylaniline, and diphenylamine. Also, it has been made clear that the compounds whose structures were previously assigned to the tetraaminoethylenes, obtained from 1,1-dimethoxytrimethylamine or ethyl orthoformate and secondary amines are the corresponding triaminomethanes. It has been found that TPE and TME reacted with halogens, halogen-, nitrocompounds, and aromatic carboxylic acids to form mainly the corresponding oxamidinium salts.
Optical Activity of Bis-1,1′-spiroindanes. II. Absolute Configuration of Optically Active 5,5′- and 6,6′-Disubstituted-bis-1,1′-spiroindanes and Their Circular Dichroism Spectra
Authors: Hagishita Sanji , Kuriyama Kaoru , Shingu Keiji , Nakagawa Masazumi
Published: July 2006

An unequivocal determination of the absolute configuration of 5,5′- and 6,6′-disubstituted bis-1,1′-spiroindane and the behavior of the CD spectra of some 5,5′-disubstituted ones are described.
Synthesis of Poly Substituted cis-Hydrindanes
Authors: Yamamoto Kagetoshi , Sohda Takashi , Kawasaki Ichiro , Kaneko Takeo
Published: July 2006

cis-4-Carboxy-5-isopropyl-8-methylhydrindane-1,6-dione was synthesized from cis-1-hydroxy-8-methylhydrindanone-5 as a useful intermediate for the synthesis of picrotoxin and dendrobine.
Electronic Spectra of Square-Planar Bis(tertiary phosphine)dialkynyl Complexes of Nickel(II), Palladium(II), and Platinum(II)
Authors: Masai Haruo , Sonogashira Kenkichi , Hagihara Nobue
Published: July 2006

Electronic spectra of trans-[L2M(C≡CR)2], (L=tertiary phosphine or tertiary stibine, and M=Ni, Pd or Pt) have been studied in solution from 220 mμ to 360 mμ. Nickel and platinum complexes showed three intense absorption bands. The lowest energy band was particularly sensitive to substituents of alkynyl groups. This band was assigned empirically to the transition between the molecular orbitals involved in metal-alkynyl bonds. The possibility of π-interaction between the two alkynyl groups through central metal was discussed in relation to the influence of R.
Electron-transfer Phenomena in Some Three-dimensional Complex Thiocyanate Semiconductors
Authors: Hashimoto Masao , Kawai Shichio , Kiriyama Ryôiti
Published: July 2006

Measurements of the electrical conductivity, the photoconductivity, the electronic spectra, and the magnetic susceptibility were carried out with powder samples of CuHg(SCN)4 and (CuxZn1−x)Hg(SCN)4. The electrical conductivity (σ) of the compounds has been found to obey the usual exponential equation of electrical conduction, σ=σ0exp(−Et⁄KT). It was found that there was a close relation between the photocurrent spectra and the electron-transfer bands in both compounds. In terms of the band model, the nature of the semiconductivity and the photocurrent in their intrinsic region are discussed in connection with the electron-transfer phenomena.
Elimination Reaction on Solid Acid Catalysts. IV. A δR LFER Study of the Esterification of Alcohols with Carboxylic Acids over Solid Acid Catalysts
Authors: Mochida Isao , Anju Yasuhide , Kato Akio , Seiyama Tetsuro
Published: July 2006

The esterification between eight alcohols and seven carboxylic acids was studied over sodium-poisoned silicaalumina at 250°, using a microcatalytic gas chromatographic technique, in order to elucidate the mechanism of the esterification on a solid acid catalyst on the basis of a LFER (Linear Free-Energy Relationships) approach. Alcohols showed fairly close reactivities for the esterification with acetic acid, whereas, for the olefin formation by intramolecular dehydration and ethylether formation with ethanol, their reactivity varied very much according to the kind of alcohol. In contrast, the reactivities of carboxylic acids for the esterification varied with the structure and were correlated with Es, Newman’s steric-effect parameter, as was observed in the homogeneous acid catalysis, although the reactivity difference under the present conditions was small indeed. It is probably due to the elevated reaction temperature. No ethylacetate, but only thiolacetate, was found in the reaction of acetic acid with ethanethiol. From these facts, it may be concluded that the esterification over a solid acid catalyst may proceed through the attack of an oxonium ion from a carboxylic acid on an adsorbed alcohol, in the manner similar to that in the homogeneous acid-catalyzed esterification.
Rearrangement and Decomposition of Phosphoranyl Peroxides Produced in situ from Alkylidenephosphoranes and t-Alkylperoxy Anions
Authors: Yamada Koh-ichi , Akiba Kin-ya , Inamoto Naoki
Published: July 2006

The reactions of alkylidenephosphoranes(I), produced in situ from the corresponding phosphonium salts and sodium ethoxide, with sodium salt of t-butyl hydroperoxide (II) were carried out in absolute ethanol. Carbanion (III) of phosphoranyl peroxide, formed by the reaction of I with II, underwent a rearrangement to produce t-butyl phenyl ether, alkyl t-butyl ether, and two kinds of phosphine oxides. Phosphoranyl peroxide (IV), formed by abstraction of proton from ethanol, decomposed in homolytic fashion to yield t-butyl alcohol and hydroxyphosphorane (V) as an intermediate, the decomposition of which gave benzene, hydrocarbon and corresponding phosphine oxides. Homolytic decomposition of IV was supported by the reaction of tetraphenylphosphonium bromide with II. The contribution of III was confirmed by the effect of base concentration on the amounts of rearrangement products. The reaction with cumylperoxy anion gave similar results. The mechanisms of these reactions were discussed.
Cyclopropenones. IV. The Reactions of Diphenylcyclopropenone with Water, Carboxylic Acid, Phenol, and Amide
Authors: Toda Fumio , Kataoka Toshiaki , Akagi Katsuhiko
Published: July 2006

The pyrolysis of diphenylcyclopropenone monohydrate (II) at 150°C afforded α-phenyl-trans-cinnamic anhydride (VI). It was proved that the reaction consists of two main steps, the nucleophilic attack of water on I to yield α-phenyl-trans-cinnamic acid (IV), and the reaction of I with IV, thus finally yielding VI. The same type of reaction as that of I with IV was also observed when I was heated in phenol to afford phenyl α-phenyl-trans-cinnamate (XII). The reaction of I with the weak nucleophilic reagent, α-phenyl-trans-cinnamamide (XIV), afforded a monoimino derivative of VI (XVI), which is believed to be produced by the nucleophilic attack of the amide-oxygen of XIV on the carbonyl-carbon of I.
The Preparation of Geometrical Isomers of β-Nitrostyrene and Their Addition Reactions with Ethanol
Authors: Yamamura Kimiaki , Watarai Setsuo , Kinugasa Toshio
Published: July 2006

The preparation of the geometrical isomers of ethyl α-nitrocinnamate and α-nitrochalcone is described. Ethyl (E)-α-nitrocinnamate and (Z)-α-nitrochalcone were obtained by the thermal- or photoisomerization of the corresponding geometrical isomers, which were themselves produced predominantly through the Knoevenagel reaction. The facile addition of ethanol to the double bonds of β,β-dinitrostyrene, ethyl α-nitrocinnamates, and α-nitrochalcones without any catalyst at room temperature is also described.
The Preparation of Amino-s-triazines with Amino- or Nitrophenyl Groups
Authors: Yuki Yasuo , Kakurai Toshio , Noguchi Tatsuya
Published: July 2006

Amino-s-triazines with nitro groups were prepared by the reaction of biguanide derivatives with appropriate carboxylic acid derivatives (acyl chloride, anhydride, or ester) or by reaction between dicyanodiamide derivatives and nitrile. Amino-s-triazines with aminophenyl groups were prepared by the reduction of the corresponding nitro-compounds. Acylamino-s-triazines have been found to be formed when an excess of acyl chloride or anhydride is used.
Syntheses and Thermal Isomerizations of Bicyclo[3.2.2]nona-2,6,8-triene and Its Benzo Analog
Authors: Tsuji Teruji , Ishitobi Hiroyuki , Tanida Hiroshi
Published: July 2006

A convenient synthesis of bicyclo[3.2.2]nona-2,6,8-triene (1) was devised starting from the cycloheptatrienemaleic anhydride adduct. Benzo[f]bicyclo[3.2.2]nona-2,6,8-triene (2) was prepared starting from benzo[f] bicyclo[3.2.2]nona-3,6,8-trien-2-one. Heating 1 in n-hexane at 160–180°C gave almost quantitatively 3-vinyl-cycloheptatriene (9) besides a trace of 7-vinylcycloheptatriene (10). It was found however that 10 undergoes thermal isomerization into 9 under milder conditions. The result from 1 is thus rationalized by the existence of an equilibrium between 1 and 10 preceding the conversion of 10 into 9. On the other hand, benzo analog 2 does not isomerize in a similar manner and instead, is transformed by heating at 270–290°C into benzobarbaralane (14) and hydrobenzindene (15). The contrast in behavior is discussed.
The Reactions of β-Ketosulfonium Salts with Sulfenamide Derivatives
Authors: Mukaiyama Teruaki , Hosoi Kazuo , Inokuma Shun , Kumamoto Takanobu
Published: July 2006

2-Phenylthio-2-(dimethylsulfuranylidene)acetophenone was obtained in good yield by the reaction of dimethylphenacylsulfonium bromide with N,N-diethylbenzenesulfenamide. The reaction of dimethyl-α-methylphenacylsulfonium bromide with N,N-diethylbenzenesulfenamide gave α-phenylthioacrylophenone in good yield. The reactions of α-phenylthioacrylophenone thus obtained with various active methylene compounds were investigated.
Synthesis and Properties of Two Annelated Annulenes
Authors: Endo Katsusuke , Sakata Yoshiteru , Misumi Soichi
Published: July 2006

Two annelated tridehydrof[18]annulenes, trinaphtho[1,9,8,7-abc: 1′,9′,8′,7′-ghi:1″,9″,8″,7″-mno]- and tribenzo[a,g,m]-5,11,17-tridehydro[18]annulenes (VI and VII), were synthesized by the Castro reaction of cuprous salts of 1-ethynyl-7-iodonaphthalene (IX) and 4-[o-iodophenyl]-3-buten-1-yne (XIV), respectively. The UV spectra of these annelated annulenes revealed an extended delocalization of π-electrons around the inner eighteen membered ring. However, from the chemical shifts of the inner protons (HA and HB) it is concluded that both VI and VII are non-aromatic compounds.
Decomposition of m-Nitrobenzenesulf onyl Peroxide in Several Solvents
Authors: Yokoyama Yasukazu , Wada Hiroko , Kobayashi Michio , Minato Hiroshi
Published: July 2006

Rates of decomposition of m-nitrobenzenesulfonyl peroxide in chloroform, nitrobenzene, chlorobenzene, and benzene were determined, and activation parameters were calculated. Products of decomposition in nitrobenzene were m-nitrophenyl m-nitrobenzenesulfonate and m-nitrobenzenesulfonic acid, whereas those in chloroform were m-nitrobenzenesulfonic acid, hexachloroethane, and phosgene (when air is present). Activation parameters and reaction products indicate that the reaction in chloroform involves homolytic cleavage of the O–O bond, whereas that in nitrobenzene involves electrophilic attack of the peroxide on aromatic nuclei. When sulfonyl-18O labeled m-nitrobenzenesulfonyl peroxide was decomposed in benzene, about 35–36% of the label was found in the phenolic oxygen of m-nitrophenyl m-nitrobenzenesulfonate. This finding could be accounted for by a mechanism which involves a loose π-complex prior to the formation of a σ-complex.
Phenylazo p-Tolyl Sulfone as a Source of Phenyl Radical
Authors: Kobayashi Michio , Minato Hiroshi , Kojima Minoru , Kamigata Nobumasa
Published: July 2006

Mechanism of the decomposition of phenylazo p-tolyl sulfone(I) was investigated. Orientations and partial rate factors of substituted biphenyls produced by the decomposition of I in benzene-substituted benzene mixtures were used as the criteria for judging the nature of the decomposition. When CaO- or MgO-suspension was present, autocatalytic heterolysis of I was suppressed to some extent, but for complete suppression 20–40 w/v % CaO or MgO was necessary. Pyridine and quinoline were found to be effective for suppression of the autocatalysis. When sufficient amount of pyridine, quinoline, MgO or CaO were present, orientations and partial rate factors for phenylation of substituted benzene were similar to those obtained by phenyl radical produced by benzoyl peroxide on N-nitrosoacetanilide. The rate of decomposition of I was determined in PhC2H5, PhOCH3, PhCl, PhNO2, pyridine and DMF in the presence of pyridine. An isokinetic relationship was found to hold for activation parameters for the decomposition in these solvents, and the isokinetic temperature was 88.6°C. Values of activation enthalpy and entropy were rather large; ΔH\eweq=39.6 kcal/mol and ΔS\eweq=34.4 e.u./mol in DMF.
Photoconduction of Polystyrylpyrimidines
Authors: Hirohashi Ryo , Hishiki Yasushi , Haruta Masahiro
Published: July 2006

Eight polystyrylpyrimidines were synthesized from p-xylylpyrimidine with p-phenylene diisothiocyanate (DIT), terephthaloylchloride (TPC), p-xylylenedibromide (XDB), p-phenylenediamine (PDA), 4,4′-diaminodiphenyl (BD), 4,4’-diamino diphenylsulfone (DPS), hexamethylene diamine (HMD), and 4,4′-diaminodiphenylmethane (DPM). These polymer films have a fairly large photoconductive character; using a surface-type photoconductive cell, the logarithmic relation of the photo-current (Ip) to the applied potential was found to be linear. Further, it was found that the slopes (n) obtained from the logarithmic relation (Ip=kLn) of the photo-current to the light intensity (L) have values from 1.0 to 2.4. The peaks of the spectral response of the photo-current of the eight samples exit around 500–600 mμ and/or near the ultraviolet wavelength region. The photoconduction of these polymers was enhanced by the bridging groups attached to xylylpyrimidine; the enhancement is in the following order;

(Remark: Graphics omitted.)
The Preparation of Fukinane, A New Skeletal Sesquiterpene Hydrocarbon
Authors: Naya Keizo , Kobayashi Masakazu
Published: July 2006

A novel skeletal sesquiterpenic hydrocarbon, fukinane (I), has been prepared by conversion from an eremophilane type, fukinone (VIII), via fukinan-8-ol (IX). A rearrangement of the fukinane skeleton into an eremophilane type through fukinan-8-ol tosylate (X) has been studied.
The Measurement of Reaction Rates under Pressure by using a Manganin Pressure Gauge
Authors: Moriyoshi Takashi
Published: July 2006

An apparatus capable of following reaction rates under pressure without sampling has been designed and constructed. The pressure change due to the progress of a reaction in a closed system could be accurately measured to about 0.08 atm by means of a “fixed bridge” combined with a manganin pressure gauge, in which the unbalanced e.m.f. generated at a constant bridge current was potentiometrically determined to 0.1 μV. The rates of the acid-catalyzed inversion of sucrose and the base-catalyzed decomposition of diacetone alcohol, with the expansion in volume and the contraction respectively, were measured in order to verify the applicability of this apparatus. The agreement between the results obtained by this method and those obtained by the analytical method was satisfactory. From these results, it has been confirmed that the method is sufficiently applicable to the measurement of reaction rates under pressure.
Stochastic Formulation of Entropy Production due to Second-Order Reaction
Authors: Ishida Kenji
Published: July 2006

Entropy production, originated from an ideal gas second-order reaction taking place in a closed system, has been stochastically formulated by defining the entropy in a form similar to the conditional entropy used in the theory of information. The entropy is introduced in the natural way as a result of the partial factorization of joint probability for reaction states devised for the approximate solution of the stochastic process of the second-order reaction. The entropy production has also been discussed in comparison with the usual one.
The Reactions of Mobile Electrons in the Frozen Solution of Ethylene Glycol-Water at 77°K
Authors: Sasaki Teikichi , Ohno Shin-ichi
Published: July 2006

The yield of trapped electrons produced in ethylene glycol-water glass at 77°K increased linearly with the gamma dose up to 1.5×1020 eV/g, and the G value was estimated to be 2.8±0.2. The relative reaction rates of mobile electrons with various inorganic ions at 77°K were determined by competition kinetics. The observed relative reaction rates with simple inorganic ions corresponded to those of hydrated electrons obtained at room temperature. For complex ions, however, the reactivities of the mobile electrons were larger than those of hydrated electrons. The reaction products, such as bromine dioxide, Cr(V) species, and the pentacyano Co(II) ion, all of which are unstable at room temperature, could be detected by optical and ESR spectroscopies at 77°K.
The Electronic Character of the π-Allylic Group of π-Allylic Palladium Complexes
Authors: Takahashi Yasutaka , Akahori Hiroyuki , Sakai Shizuyoshi , Ishii Yoshio
Published: July 2006

The substituent constants of the 2- and 1-positions of the π-allylic group of acetylacetonato (a) and cyclopentadienyl (b) derivatives of π-[2-(p-substituted phenyl)allyl]-(I) and π-(p-substituted cinnamyl)-palladium complexes(II) were estimated from their NMR spectra. The differences in the chemical shift (Δν, Hz) between the p-phenylene ring protons H1 and H2 of the complexes was found to be dependent upon the ligand and the substituent X. The plot of Δν against the substituent constant σp+, of X gave a fairly good linear relationship, and from the intercept of the straight line at Δν=0, the substituent constants of the 1-and 2-positions of the π-allylic group in the IIa or IIb complex and the Ia or Ib complex were estimated: σp: at the 1-position, 0.27 (IIa) or 0.24 (IIb), and at the 2-position, 0.21 (Ia) or 0.03 (Ib).
A Convenient Method for the Preparation of Primary Amines by the Use of Bisbenzenesulfenimide and Bis-p-chlorophenylsulfenimide
Authors: Mukaiyama Teruaki , Taguchi Takeo , Nishi Mineo
Published: July 2006

A convenient method for the preparation of primary amines by the use of bisarylsulfenimide has been established. Primary amines were obtained in good yields under mild reaction conditions by treating N-substituted bisarylsulfenimides with hydrochloric acid or mercaptan. The N-substituted bisarylsulfenimides were prepared in good yields by the reactions of lithium bisarylsulfenimide with alkyl halides or alkyl p-toluenesulfonates or by the addition reactions of bisarylsulfenimide to olefinic compounds.
Aminocyclitols. XXVII. Preparation of Deoxyinosamines from vibo-Quercitol
Authors: Suami Tetsuo , Ogawa Seiichiro , Yabe Kenji , Uchida Masaru
Published: July 2006

On bromination with acetyl bromide and acetic anhydride at 130°C, vibo-quercitol (1) gave tetraacetyl 1-bromo-1-deoxy-scyllo-quercitol (2) in 23% yield. Treatment of 2 with sodium azide in an appropriate solvent afforded three azido compounds, from which, by hydrogenation, corresponding three deoxyinosamines were obtained: 1-deoxy-scyllo-2, 5-deoxy-chiro-1 and 1-deoxy-myo-2-inosamine. The latter two are new compounds and their structures were established by their proton magnetic resonance (PMR) spectra and the reaction sequences.
Selective p-Toluenesulfonylation of myo-Inositol Derivatives
Authors: Suami Tetsuo , Ogawa Seiichiro , Oki Shuichi
Published: July 2006

Attempt to know the reactivities, toward sulfonylation, of the hydroxyl groups in myo-inositol was carried out using partially sulfonylated derivatives of myo-inositol. The present studies indicated that the order of reactivity of the hydroxyl groups is 1-OH and 3-OH>4-OH and 6-OH>5-OH>2-OH. From a preparative standpoint, 1,3–di-O-p-toluenesulfonyl-myo-inositol was readily obtained in 59% yield from 1-O-p-toluenesulfonyl-myo-inositol by a selective sulfonylation.
Stereochemical Studies of Monoterpene Compounds. XII. The Acid-Catalyzed Rearrangements of 2α-Bromo-10β-pinan-3-one
Authors: Hirata Toshifumi , Suga Takayuki
Published: July 2006

In connection with the bromination of 3-acetoxy-pin-2-ene (II), the acid-catalyzed rearrangement of 2α-bromo-10β-pinan-3-one (I) was investigated under several conditions. The bromoketone (I) was thus found to yield (+)-6-endo-bromocamphor (III), (−)-α-carvone (V), (−)-8-hydroxycarvotanacetone (VI), carvacrol (VII), (+)-dihydro-β-campholenolactone (VIII), and (+)-campholenic acid (IX). It also became clear that the bromocamphor (III) and the (V), (VI), and (VII) products are directly formed from the bromoketone (I), whereas the γ-lactone (VIII) is obtained via α-campholenic acid (IX) from the bromocamphor (III). The mechanistic implications of the rearrangements are discussed.
Studies of N-Sulfinyl Compounds. VI. The Preparation of N-Sulfinylbenzamide and Its Reaction with Styrene Oxide
Authors: Tsuge Otohiko , Mataka Shuntaro
Published: July 2006

The reaction of benzamide with thionyl chloride in the presence of pyridine gave N-sulfinylbenzamide and N,N′-dibenzoylsulfurdiimide. It has been found that N-sulfinylbenzamide reacted with styrene oxide in the presence of tetraethylammonium bromide to give 4-oxo-5-benzoyl-2,6-diphenyl-1,4,3,5-oxathiadiazepine as the main product, accompanied by lesser quantities of two N-benzoyl-phenylaminoethanols, 2,5-diphenyloxazoline, benzonitrile, and benzamide. The pathways for the formation of the products are suggested.
Reaction of Methanol with Accelerated Rare Gas Ions
Authors: Kotoyori Takashi , Takahasi Makoto , Ichinose Akira
Published: July 2006

Reaction of methanol with accelerated rare gas ions was studied. The yields of the reaction products, H2, CO, CH4, HCHO, and ethylene glycol, were determined, varying the initial kinetic energy of ion (2–6 kV), ionic species, (Ar, Xe, and Kr), and pressure of methanol ((2–14)×10−3 Torr). No appreciable effect on the product yields was observed by adding carbon tetrachloride as electron scavenger or propylene as radical scavenger. The product yields are found to be linear against In Ei, (Ei is initial kinetic energy of ions). Although the detailed reaction mechanism is left for future investigation, the reaction seems to be interpreted in terms of billiard model, momentum of ion being transferred directly to a local part of the target molecule at the contact time.
Structure and Rotational Isomerism of Ethylenediamine as Studied by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo
Published: July 2006

The structure and the rotational isomerism of ethylenediamine have been investigated by means of gas electron diffraction. Evidence has been given for the presence of one conformer (gauche) in the vapor phase (at 50–120°C); the N–C–C–N dihedral angle measured from the cis position is 64·0±4°, and the fraction of any other isomer, if present, is estimated to be less than 5%. A theoretical prediction based on the SCF-CNDO/2 method has essentially accounted for this finding. The rg distances and the angles based on the ra structure determined by a least-squares analysis on molecular intensities, with estimated limits of error, are as follows: C–C=1.545±0.008 Å, C–N=1.469±0.004 Å, ∠C–C–N=110.2±0.7°, C–H=1.109±0.01 Å, ∠C–C–H=111·9±5°, and ∠H–C–H=112·7±8°.
The Crystal Structure of 1,4-Bis(p-bromophenoxy) butane
Authors: Ishikawa Toshihiko , Karino Seiichi , Nagai Susumu , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The structure of 1,4-Bis(p-bromophenoxy) butane has been determined by means of a single-crystal X-ray analysis. The compound crystallizes in the monoclinic space group Cc, with four molecules per unit cell: a=13.426, b=15.249, c=7.650 Å, and β=89.39°. The structure has been solved by the heavy-atom method. The final discrepancy index is 0.068 for 970 non-zero reflections. The conformation of the methylene chain in the –O(CH2)4O– group is gauche-trans-gauche, with internal rotation angles of 61.0, 181.0, and 55.2° respectively.
Reactions of Aliphatic Amines with p-Benzoquinone and Its Chloro Derivatives
Authors: Yamaoka Tsuguo , Nagakura Saburo
Published: July 2006

The reactions of various aliphatic amines with p-benzoquinone and its chloro-derivatives were studied by detecting reaction intermediates by means of the rapid scan spectrophotometric method. A detailed kinetic study on the reaction intermediate and the final product was made for the system including n-butylamine and chloranil in ethanol; the result shows that the system produces 2,5-di-n-butylamino-3,6-dichloro-p-benzoquinone via the chloranil anion and the n-butylamine cation with the rate constant of 9.8×102 sec−1mol−1l at 275.2°K. On the basis of reaction mechanisms, the reactions of various aliphatic amines with p-benzoquinone and its chloroderivatives were classified into five types. Stabilization energies due to the amino-substitution of p-benzoquinone were calculated by the composite molecule method; the result shows that the 2,5-derivative is most stable among the disubstituted p-benzoquinones.
The Phase Equilibria in the FeO-Fe2O3-V2O3 System at 1500°K
Authors: Wakihara Masataka , Katsura Takashi
Published: July 2006

The phase equilibria in the FeO–Fe2O3–V2O3 system have been determined at 1500°K by varying the oxygen partial pressure. The following three oxide phases have been stable in equilibrium: a sesquioxide solid solution with a corundum-type structure (approximate composition Fe2O3–V2O3), a ternary solid solution with a spinel type structure (approximate composition FeO·Fe2O3–FeO·V2O3), and a ternary wüstite solid solution with a periclase-type structure which dissolves vanadium ions up to about 10 mol per cent. The extent of the solid solution areas and the location of the oxygen isobars have been determined. The spinel phase coexisted partly with metallic iron and partly with the wüstite solid solution, corresponding to lower and higher iron contents respectively. The standard free energies of the Fe+V2O3+\frac12O2=FeV2O4 and 0.05 Fe+V2O3+Fe0.95O=FeV2O4 reactions to produce FeV2O4 have been calculated to be −45500±200 cal and −5800±400 cal respectively at 1500°K on the basis of the equilibrium oxygen partial pressure.
SN2 Reactions in Dipolar Aprotic Solvents. Chlorine Isotopic Exchange Reactions of 2-Arylethyl Chlorides, Chloromethyl Aryl Ethers, and Chloromethyl Aryl Sulfides in Acetonitrile
Authors: Hayami Jun-ichi , Tanaka Nobuo , Kurabayashi Syuji , Kotani Yasuhiro , Kaji Aritsune
Published: July 2006

The SN2 reactions having a symmetrical transition state were studied in a dipolar aprotic solvent. A good Hammett correlation was found for the chlorine isotopic exchange reactions in acetonitrile between tetraethylammonium chloride and three types of substituted methyl chlorides, 2-arylethyl chlorides, chloromethyl aryl ethers, and chloromethyl aryl sulfides. The reaction constant was positive for 2-arylethyl chlorides and negative for the methyl chlorides possessing an α-heteroatom. The presence of oxygen and sulfur atom on the α-position to the reaction center resulted in a rate enhancement of about 105 times and 103 times, respectively. Features of the transition states of these SN2 reactions are discussed.
Polymerization of Methyl Methacrylate by the Bis(benzoylacetonato)Copper(II)-1,10-Phenanthroline System
Authors: Kaeriyama Kyoji , Yamazaki Yukio
Published: July 2006

The addition of 1,10-phenanthroline accelerates the polymerization of methyl methacrylate by a β-diketonato chelate of Cu(II), Mn(II), Mn(III), Co(II), Co(III), and Fe(III), but has no effect on the chelate of Ni(II). The effect of 1,10-phenanthroline, which is composed of two pyridine units, is much greater than that of pyridine. The polymerization rate of methyl methacrylate by the bis(benzoylacetonato)Cu(II)-1,10-phenanthroline system may be represented as follows:

R p∝ [MMA]{[Cu(II)][1,10-phenanthroline]}1⁄2

The initiation reaction is assumed to be by a ligand-exchange reaction of bis(benzoylacetonato)Cu(II) with 1,10-phenanthroline, where a benzoylacetonyl ligand is displaced by 1,10-phenanthroline and Cu(II) is simultaneously reduced to Cu(I).
The Properties and Assignment of Isomers of 2,4-Dinitrophenylhydrazones of Some Aliphatic α-Keto Acids
Authors: Katsuki Hirohiko , Yoshida Tsuya , Nagai Jun , Tanaka Shozo
Published: July 2006

Visible and infrared spectra and some other properties of cis and trans isomers of 2,4-dinitrophenylhydrazones of some aliphatic α-keto acids have been studied. It was observed that absorption maximum of the cis isomer in visible region occurred at a longer wavelength than that of the trans isomer in ethyl acetate as well as in bicarbonate solution and vice versa in sodium hydroxide solution. In infrared region, N–H and C=O stretching bands of the cis isomer were found at longer wavelengths than the corresponding bands of the trans isomer. It was concluded that a hydrogen bond is formed between C=O and N–H groups in the cis isomer. Further evidence which supports the above conclusion was given by the difference between both isomers in the nickel complex forming reaction, sodium carbonate reaction and in the properties of sodium salt. Instability of the trans isomer appeared to increase as the number of carbon atoms in the keto acid molecule increased. 2,4-Dinitrophenylhydrazones of some other α-keto acids were found to give polymorphs but not geometrical isomers.
The N–H Stretching Absorption Band Intensities in Secondary Amides, Secondary Thioamides, and Anilides
Authors: Bai P Usha , Ramiah K Venkata
Published: July 2006

The intensities of the N–H stretching absorption bands of a number of N-methylamides, N-methylthioamides and anilides have been measured in a solution of carbon tetrachloride. It was observed that the intensities of the N–H stretching absorption bands of N-methylacetamide and N-methylpropionamide are considerably higher than those of the same band in the corresponding anilides. On the other hand, the intensity of the N–H stretching absorption band of N-methylformamide is of the same order as that of formanilide. The pattern of variation of the intensity of the N–H streching absorption bands in these compounds is similar to that of the C=O stretching absorption bands of the same compounds, but the variation in their frequencies is different. It was also observed that the intensities of the N–H stretching bands of N-methylthioamides are considerably higher and their frequencies are lower than those of the corresponding secondary amides.