bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Constituents of the Male Flower of Alnus pendula (BETULACEAE)
Authors: Suga Takayuki , Iwata Nobuo , Asakawa Yoshinori
Published: July 2006

The structure of alnustone (1) isolated from the male flower of Alnus pendula Matsum. has been established to be 1,7-diphenyl-1,3-heptadien-5-one. Previously-known compounds, β-phenylethyl cinnamate (6), cinnamaldehyde, benzylacetone, β-phenylethyl alcohol, pinocembrin (7), pinostrobin (8), alpinetin (9), galangin (11), pinosylvin (13), and its monomethyl ether (14), eugenol, chavicol, cinnamic acid, β-phenylpropionic acid, and benzoic acid, were identified along with the above new ketone.
ESR of Hot Ions: Zn(I), Cd(I), and Hg(I) in γ-Irradiated Potassium Tetracyano Zincate(II), Cadmate(II), and Mercurate(II)
Authors: Isoya Jun-Ichi , Fujiwara Shizuo
Published: July 2006

It is known that X-ray or γ-ray irradiation of inorganic complexes produces hot ions which have lower valence states than the original ones and yet are sited in the regular crystalline array of the undamaged mother complexes. ESR study reveals that the hot ions of paramagnetic Zn(I), Cd(I), and Hg(I) complexes are formed by γ-irradiation of K2[Zn(CN)4], K2[Cd(CN)4], and K2[Hg(CN)4], respectively. Hyperfine structures of the ESR signals shows that the Zn(I) and Cd(I) complexes have C3v, symmetry instead of Td symmetry of the original complex, and Hg(I) complex has a slightly distorted C3v symmetry. In Zn(I) complex, one of the four symmetry axes along Zn(II)–CN bondings is stretched. This occurs evenly with respect to each axis, resulting in the formation of four sites of the electron spins. For Cd(I) complexes, four species are produced as an irradiation product, where each species has four sites which are axially symmetric with respect to any one of the four Cd(II)–CN bondings. In Hg(I) complex, there exist twenty-four sites and the symmetry axis of each site lies along a direction slightly deviated from the original Hg(II)–CN bonding. From the behavior of the decay of ESR signal intensity at liquid nitrogen temperature, it is concluded that the stability is in the order Hg(I)>Cd(I)>Zn(I).
Dimerization of Ethylene Catalyzed by σ-Aryl Nickel Compound in the Presence of Trifluoro Boron Etherate
Authors: Maruya Ken-ichi , Mizoroki Tsutomu , Ozaki Atsumu
Published: July 2006

It was found that σ-aryl nickel(II) complex catalyzes the dimerization of ethylene rapidly and selectively when trifluoro boron etherate is added. The rate of dimerization increases in order Br<<mesityl<naphthyl<o-tolyl. The aryl ligands remain in the nickel complexes during the course of dimerization, since vinyl naphthalene, butenyl-naphthalene, etc., which are expected to be the reaction products of ethylene with the σ-aryl lingands, were not detected. The isotopic exchange between ethylene and deuteroethylene and the dimerization of deuteroethylene were studied to confirm the active species of this catalyst system. The isotopic exchange is faster than both the dimerization and isomerization of 1-butene formed. No increase in the atomic fraction of hydrogen of deuteroethylene was observed after treatment with the catalyst system. Thus it is concluded that the nickel hydride formed by the dissociative addition of ethylene is the active species of the catalyst system. The role of trifluoroboron etherate was also elucidated by a comparison of its effect on the rate of ethylene dimerization with that of sodium tetraphenyl borate.
The Orientation Overgrowth of Polycyclic Aromatic Quinones on the Cleavage Surface of Alkali Halide Single Crystals
Authors: Ashida Michio , Hamada Akihiko , Watanabe Teizo
Published: July 2006

Vacuum-condensed films of polycyclic aromatic quinones (flavanthrone, indanthrone, and pyranthrone) were found to grow epitaxially on the cleavage faces of NaCl and KCl. Electron microscopy studies have shown that all the films on NaCl were composed of small, needle-like crystallites crossing orthogonally. The needle axis of the crystals coincides with the 〈110〉 directions of NaCl. When a cleavage surface of KCl was used as the substrate, vacuum-condensed films of flavanthrone and indanthrone were composed of dendroid crystals which assumed the standing b-axis orientation with an apparent C4v symmetry. On the other hand, a pyranthrone film on KCl was composed of wedge-like crystals which assumed the standing b-axis orientation. The electron-diffraction pattern of the film revealed that the b-axis of each crystal tilts against the normal of the substrate face at an angle of 29° and takes a random orientation. When the films assume the standing b-axis orientation, the planar molecule in the crystal comes into parallel contact with the cleavage face of KCl. It may be presumed that the nitrogen atoms in both flavanthrone and indanthrone molecules are placed on potassium ions in the (001) plane of KCl.
The Surface Properties of Rutile Prepared by the Hydrolysis of Titanium Tetrachloride. I. The Heat of Immersion in Water
Authors: Iwaki Toru , Komuro Masayoshi , Miura Masaji
Published: July 2006

The surface properties of rutile prepared by hydrolyzing titanium tetrachloride have been studied by measuring the heat of immersion in water as a function of the outgassing temperature. The heat of immersion showed an extremely large value at outgassing temperatures between 300 and 400°C. However, when the rutile was calcined at 800°C, it showed a heat-of-immersion curve similar to those hitherto reported. In order to examine the phenomenon found on uncalcined rutile, the amounts of water physically and chemically adsorbed on the surface were estimated by measuring the water-vapor adsorption. We found that hydroxyl groups were formed in bulk as well as on the surface by means of the chemisorption, resulting in the formation of a hydrous structure because of the low crystallinity of the sample at temperatures below 400°C.
Studies of the Properties of the Basic Sites on the Silica-alumina Surface through the Reaction of the Basic Sites with Copper(II) Complexes Containing 2,2′-Bipyridine
Authors: Takimoto Kazuto
Published: July 2006

The substitution reactions of complexes with basic sites on the surfaces of silica-alumina and alumina and the properties of the basic sites were studied through the adsorption of the complexes onto the surfaces. The hydroxyl groups with basic strengths of two kinds, H0>9.3 and 7.2<H0<9.3, exist on the silica-alumina surface pretreated at 300°C. They are present in a cluster state. The basic strength becomes higher as the outgassing temperature becomes lower. The complexes predominantly interact with the O2− ions on the surface pretreated at a relatively high temperature, resulting in new chemical species. The basic strength of the O2− ions is lower than that of the hydroxyl groups on the surface pretreated at a lower temperature. The hydroxyl groups on the alumina surface outgassed at 300°C are distributed, on the whole, homogeneously in comparison with those of the silica-alumina surface, and their basic strength is H0>9.3. The nature of the basic sites on the alumina surface tends to vary with the outgassing temperature, similarly to those on the silica-alumina surface. These analyses were performed on the basis of the ESR spectra for complexes in basic solutions.
Studies on Nucleosides and Nucleotides. II. Selective Acylation of 5’-Hydroxyl Group of Thymidine
Authors: Mitsunobu Oyo , Kimura Junji , Fujisawa Yoshiyuki
Published: July 2006

Treatment of thymidine and either acetic acid or benzoic acid with diethyl azodicarboxylate (1) and triphenyl-phosphine (2) in dioxane afforded 5′-O-acetyl or 5′-O-benzoyIthymidine along with a trace of 3′,5′-di-O-acylated product. When thymidine and benzoic acid or p-substituted benzoic acids were allowed to react with 1 and 2 in hexamethylphosphoric triamide(HMPA), the corresponding 5′-O-aroylthyinidines were selectively obtained. The aroyl groups having electron-withdrawing substituents were much more readily removed than those having electronreleasing groups under mild alkaline conditions.
Synthesis of Tengerite Type Rare Earth Carbonates
Authors: Wakita Hisanobu , Nagashima Kozo
Published: July 2006

Rare earth carbonates which give the same X-ray powder diffraction pattern as tengerite were prepared by heating aqueous solutions containing rare earth chlorides and ammonium trichloroacetate. Y, Er, Ho, and Gd gavee xactly the same X-ray powder pattern as tengerite, while Nd and Sm were similar to tengerite but with a few additional diffractions. X-ray powder data of the tengerite type rare earth carbonate were indexed and cell parameters of a0=9.20±0.02 Å, b0=11.32±0.03 Å, and c0=7.59±0.01 Å for Y2(CO3)3·nH2O (n=2–3), with 4 moles of formula units per cell and orthorhombic symmetry were established. Linear correlations were demonstrated between refractive indices or cell parameters of the synthesized carbonates and their respective rare earth element atomic numbers.
Preparation and Circular Dichroism Spectra of Bis(aminoacidato)ethylenediaminecobalt(III) Complexes
Authors: Matsuoka Nobuko , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Cis(O) and trans(O) complexes of bis(l-serinato)ethylenediaminecobalt(III) ion have been prepared and completely separated into six possible isomers by ion-exchange column chromatography. These isomers have been assigned to Λ-trans(O), Δ-trans(O), Λ-C2-cis(O), Δ-C1-cis(O), Λ-C1-cis(O) and Δ-C2-cis(O) in the elution order, on the basis of their absorption and circular dichroism spectra. Trans(O)- and C1-cis(O)-bis(glycinato)ethylenediaminecobalt(III) complexes have been resolved into their optically active isomers, and trans(O)-bis(l-alaninato)ethylenediaminecobalt(III) ion has been prepared and separated into two configurationally active isomers. The absorption and circular dichroism data of six isomers of [Co(l-ser)2en]+, two isomers of [Co(l-ala)2en]+ and two isomers of [Co(gly)2en]+ have been discussed in being compared with those of the corresponding isomers of oxalatobis(l-serinato)cobaltate(III) complex.
Ring Expansion through a 1,3-Acyl Rearrangement. Reactions of Cyclic Sulfonium Ylides with Acetylenic Compounds
Authors: Higo Moriaki , Sakashita Takeshi , Toyoda Minoru , Mukaiyama Teruaki
Published: July 2006

Ring expansion of cyclic sulfonium ylides with acetylenic compounds was investigated. It was found that a six-membered cyclic sulfonium ylide (I) gave eight-membered ring expansion products (IIIa—e) in high yields under mild conditions on treatment with acetylenic compounds (IIa—e) in dimethyl sulfoxide. In a similar manner, the reactions of five- and seven-membered cyclic sulonium ylides with II afforded ring expansion products (XIa) and (IXa—c). The ring expansion was considered to proceed through an intramolecular 1,3-acylrearrangement. It was found that, when the reaction of I and IIIa was carried out in benzene, an intermediate bicyclic sulfonium betaine (VIIa) was obtained as yellow precipitates. The properties and reactions of VIIa were investigated. It was shown that the ring expansion product IIIa gave cyclooctenone derivatives (XIIIa—c) by the reaction with some nucleophiles. IIIa was found to give diene esters (XIII, R=acyl)and diene ethers (XIII,R=alkyl) upon reaction with acyl and alkyl halides.
Asymmetric Hydrogenation of C=O Double Bond with Modified Raney Nickel. XXIV. The Effect of Unsaturated Compounds on the Asymmetric Activity of the Catalyst
Authors: Ninomiya Toshio
Published: July 2006

Dehydroacetic acid and methyl cis-3-acetoxycrotonate were picked out as trace impurities of the substrate, methyl acetoacetate. The effects of dehydroacetic acid, methyl cis-3-acetoxycrotonate, and diketene, which is the starting material for the preparation of methyl acetoacetate, on the asymmetric activities of catalysts modified with l-amino acids were examined in the hydrogenation of methyl acetoacetate. The above three compounds, when added to the hydrogenation system, raised the asymmetric activity of the catalyst. Also, simple unsaturated compounds, such as acetone and diethyl maleate, has a similar effect on the catalyst. The effects of the above unsaturated compounds on the asymmetric activities of the catalysts modified with l-amino acids were discussed, and it was suggested that the unsaturated compounds adsorb on the catalyst surface and might scavenge the asymmetrically uncontrolled active hydrogen absorbed on the catalyst surface.
β-(2,4,6-Cycloheptatrien-1-yl)ethylcarbene. The Synthesis of 9-Substituted Bicyclo[4.2.1]nona-2,4,7-trienes and 9-Substituted Barbaralanes
Authors: Tsuruta Haruki , Kurabayashi Katsuhiko , Mukai Toshio
Published: July 2006

The thermal decomposition of sodium salt of (2,4,6-cycloheptatrien-1-yl)acetaldehydes tosylhydrazone (4, 6, and 8) afforded 9-substituted bicyclo[4.2.1]nona-2,4,7-triene (9, 11, and 14) and 9-substituted barbaralane (10, 12, and 15). In the case of 8, products containing two nitrogen atoms (17 and 18) were isolated. The structure and the photochemical reaction of 17 provided strong support for the intermediacy of the tetracyclo[4.3.0.02,9.05,7]-nona-3-ene (37) derivative for the formation of the bicyclo[4.2.1]nona-2,4,7-triene derivatives. The difference in energy surface between C9H10 and C10H10 hydrocarbons was discussed.
1,2: 8,9-Dibenzo-3,10-bisdehydro[14]annulene-5,12-dione
Authors: Kojima Takashi , Sakata Yoshiteru , Misumi Soichi
Published: July 2006

An annelated[14]annulenedione (V) was prepared by the Castro reaction of cuprous salt of o-iodocinnamoylacetylene (IV) in order to examine the aromatic character of the inner fourteen membered ring. The NMR spectra of V in arsenic trichloride and deuterotrifluoroacetic acid suggest that significant downfield shift of the inner protons HB is due to a paramagnetic ring current arising from polarization of two carbonyl groups in the inner ring, compared with the spectra of a reference compound VI.
Studies on Aminosugars. XXIX. The Synthesis of 3′-O-Methylkanamycin
Authors: Umezawa Hamao , Tsuchiya Tsutomu , Muto Ryujiro , Umezawa Sumio
Published: July 2006

6-O-(3-Amino-3-deoxy-α-d-glucopyranosyl)-2-deoxystreptamine, previously synthesized, was masked with ethoxycarbonyl, isopropylidene, and benzyl groups to give 6-O-(2-O-benzyl-3-deoxy-3-ethoxycarbonylamino-4,6-O-isopropylidene-α-d-glucopyranosyl)-N,N′-diethoxycarbonyl-2-deoxystreptaniine, which was condensed with 6-azido-2,4-di-O-benzyl-6-deoxy-3-O-methyl-α-d-glucopyranosyl chloride by a modified Koenigs-Knorr reaction to give a mixture of α,α- and α,β-diglycoside compounds. Hydrogenation of the azido group and removal of the masking groups gave a mixture of 3′-O-methylkanamycin and its diastereomer. The 3′-O-methylkanamycin was devoid of antibacterial activity.
The Constituents of Hops (Humulus lupulus L.). VII. The Rapid Analysis of Volatile Components
Authors: Naya Yoko , Kotake Munio
Published: July 2006

The volatile constituents from several varieties of Hops have been investigated by the direct loading of fresh plant tissue through GC-MS. The Saaz variety was distinguished among the examined varieties by its high content of β-farnesene. Hallertau was characterized by a low content of myrcene and a high content of humulenes. Shinshu-wase differed in its high content of myrcene and its low content of humulenes. Northern Brewer was rather close to Hallertau, whereas Yakima appeared to be closely related to Shinshu-wase. The myrcene content of hop oil was observed to correlate competitively with the total amount of humulenes, caryophyllene, and farnesene. 2-Methylbutyl isobutyrate accumulates in company with myrcene. The biosynthetic implication of these relationships have been briefly discussed.
Shapes of Fundamental Bands of Liquid Carbon Disulfide, Vibrational and Reorientational Relaxations
Authors: Kakimoto Masao , Fujiyama Tsunetake
Published: July 2006

The shapes and intensities of the fundamental bands, v2 (the CSC bending) and v3 (the C–S antisymmetric stretching), were measured for liquid carbon disulfide and its chloroform solutions. The intensity data were corrected for the effect of the dielectric field at each frequency. The analyses of the v2 and v3 bands indicate that the band-widths of liquid carbon disulfide can not be explained only in terms of reorientational relaxation. It is also shown that the vibrational relaxation of the resonance type can well explain the concentration dependence of the observed band-widths. The magnitudes of the vibrational and reorientational relaxations obtained from the bandshape analyses are given. It is emphasized that the measurement of the absolute intensity is indispensable for the analyses of the infrared-band shapes of condensed phases.
Computer Simulations of the ESR Spectra of the Triplet Dimers of Bis-(N-Salicylidenemethylaminato)copper(II) in Toluene
Authors: Ghikira Makoto , Isobe Taro
Published: July 2006

It has been concluded, from computer simulations of the observed ESR line shapes, that the dimeric structure of bis- (N-salicylidenemethylaminato)copper(II) in a frozen toluene solution is similar to that in its γ-form crystals. Furthermore, the difference between the hyperfine splittings observed at both edges of the triplet spectra for ΔM=1, the large frequency dependence of the fine-structure splitting, and the additional hyperfine structures observed in the field range between the so-called low-field parallel and perpendicular lines have been found to be due to the noncoincidence of the principal axes of the g tensor with those of the fine-structure tensor.
The Photolysis of Ethoxycarbonylmethyltriphenylphosphonium Salts
Authors: Nagao Yoshihiro , Shima Kensuke , Sakurai Hiroshi
Published: July 2006

Irradiation of ethoxycarbonylmethyltriphenylphosphonium salts (IV) gave products expected to be derived from the homolytic fission of the P–CH2CO2Et or P–Ph bond. The rate of the product formation was dependent strongly on the anion species and on the solvent polarity; an oxidizable anion was effective for the photolysis and the less polar the solvent the faster the rate became. It was found through the measurement of the electrical conductance that the degree of electrolytic dissociation of IV was very low at the concentration employed in the photolysis. On the basis of these results, the photolysis of IV was confirmed to proceed through a direct charge transfer from an anion to a cation.
The Singlet-triplet Absorption Spectra of Heterocyclic Amine N-Oxides (I)
Authors: Kubota Tanekazu , Yamakawa Masumi , Mizuno Yoshiko
Published: July 2006

The singlet-triplet absorption (T1←N) spectra of pyridine N-oxide, quinoline N-oxide, isoquinoline N-oxide, and acridine N-oxide have been observed by applying the oxygen-intensification technique. The correlation between the T1←N absorption bands and the singlet-singlet (S*←N) absorption bands of these N-oxides has been established and discussed theoretically. The lowest triplet state of the N-oxides has been assigned as the π-π* transition of a 3La (CT) nature. The T1←N absorption bands obtained show a blue shift in polar solvents. The results have been compared with the case of S*←N transitions and have been reasonably explained by taking into account the contribution from the intramolecular charge transfer.
Comparison of the Electronic Spectra of Geometric Isomers. III. β-Substituted Styrenes
Authors: Fueno Takayuki , Yamaguchi Kizashi , Naka Yuji
Published: July 2006

The ultraviolet absorption spectra of cis and trans isomers of various β-substituted styrenes have been measured both in the gaseous state and in n-hexane solution. The excitation energies observed for cis isomers are either smaller or greater than those of the trans, depending on the type of β-substituents. The isomeric difference in the energy of the lowest allowed transition was found to be linearly correlated with Taft’s steric substituent constants. The electronic states of the various isomeric pairs were calculated by the LCAO–SCF–CI method of the Pariser-Parr-Pople type. The results were found to be entirely in line with the observed spectral features.
A Computer Simulation of the Oxidation Mechanism. The Liquid-phase Oxidation of Cumene Catalyzed by Triphenylsulfonium Chloride
Authors: Ohkubo Katsutoshi , Hashimoto Tohru
Published: July 2006

The mechanism of the liquid-phase oxidation of cumene (RH) catalyzed by triphenylsulfonium chloride was investigated by the computer simulation on the basis of the kinetic analysis. We will discuss particularly the initial short stage of the reaction through the time-conversions of the concentrations of components produced or consumed: R·, RO2·, ROOH, a complex between the catalyst and O2 (Cat.–O2), etc. We determined the values of the rate constants appearing in the reaction steps with a good analytic fit to the experimental results, together with the activation energies of all the reaction steps. The following relationships were found between the initial rate of the component formation, ri (component), and the initial concentration of reactants ((Cat.)i, (RH)i, and (O2)i):

ri(Cat.–O2)\simeq1.243×10−2(Cat.)i0.970(RH)i0.0(O2)i0.964 mol⁄l·min

ri(R·)\simeq4.705×10−12(Cat.)i0.648(RH)i1.886(O2)i−0.422 mol⁄l·min

ri(RO2·)\simeq5.837×10−12(Cat.)i0.316(RH)i0.509(O2)i0.737 mol⁄l·min

ri(ROOH)\simeq4.860×10−4(Cat.)i0.436(RH)i1.842(O2)i−0.850 mol⁄l·min
Electrical and Optical Properties of the Iodine Complexes of Phenoxazine, Phenoselenazine, and Benzophenothiazines
Authors: Matsunaga Yoshio , Suzuki Yukio
Published: July 2006

The electrical resistivities and Seebeck coefficients of the 2 : 3 iodine complexes of phenoxazine, phenoselenazine, and benzophenothiazines were measured as a function of the temperature. They have resistivity values at 20°C ranging from 10 ohm·cm for the phenoxazine complex to 34 ohm·cm for the benzo[a]phenothiazine complex. Employing the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron-to-hole mobility in the phenoselenazine complex was found to be 1.07 and the electron mobility was estimated as 0.26 cm2/V sec. By an examination of the vibrational spectra, the expected cation-radical character was confirmed for the complexes of phenoselenazine and benzophenothiazines. The presence of a broad electronic absorption band in the rock-salt region characteristic of low-resistivity organic semiconductors was noted in every case.
The Resonance Raman Spectrum of the Poly(vinyl alcohol)-Iodine Complex
Authors: Inagaki Fuyuhiko , Harada Issei , Shimanouchi Takehiko , Tasumi Mitsuo
Published: July 2006

The resonance Raman spectra were observed from dilute aqueous solutions of the poly (vinyl alcohol)-iodine complex, using the He–Ne 632.8 run and Ar+ ion 488.0 nm lines for excitation. Two kinds of poly (vinyl alcohol) were used; one (A) had the degree of polymerization of 500, and the other, (B) 2000. For both samples, the resonance Raman spectra taken with the 632.8 nm line are similar to that of the starch-iodine complex, the intensity of the Raman band at 155 cm−1 being strongly enhanced. This band is assigned to the antisymmetric stretching vibration of the I3− ion aligned in the helical poly(viny alcohol) molecule. On the other hand, the intensity of the Raman band at 106 cm−1 is enhanced for Sample A when the 488.0 nm line is used for excitation. This band is assigned to the symmetric stretching vibration of the I3− ion. Its overtones were observed until the sixth. It is clear that the enhancement of the intensities of the 155 and 106 cm−1 bands is closely connected with the absorption bands at 670 and 490 nm respectively.
Photolysis of Nitromethane in Gas Phase at 313 nm
Authors: Honda Koichi , Mikuni Hitoshi , Takahasi Makoto
Published: July 2006

Photolysis of nitromethane in gas phase at 313.0 nm was studied at 55°C. Methyl nitrite, formaldehyde, nitrosomethane and NO were obtained as main products, their quantum yields being determined to be φCH3ONO=0.22, φHCHO=0.20, φCH3NO=0.06 and φNO=0.10. The dependence of the quantum yields on the pressure of quenching gases such as ethylene, cis-2-butene, CO2 and NO were investigated. The quantum yields of products except formaldehyde decrease with increase in pressure of ethylene or cis-2-butene. The sensitized isomerization of 2-butene was also observed. The quantum yield of triplet nitromethane was determined by the Gundall method and compared with that by product analysis. Both give the identical value 0.6. Since φHCHO is not affected by any quencher, it is concluded that formaldehyde is formed directly from singlet excited nitromethane.
A Theoretical Aspect on the Mechanism of Thermal Dimerization of Cyclooctatetraene
Authors: Iwamura Hiizu , Morio Kazuhiko
Published: July 2006

Thermal isomerization of cyclooctatetraene to semibullvalene 6 has been studied theoretically by the MINDO methods. The reaction is predicted to be exothermic by comparison of the calculated heats of formation and to be allowed as a concerted cyclization by constructing a complete MO correlatiom diagram. These findings together with the knowledge of thermal interconversion of cyclooctatetraene and bicyclo[4.2.0]octa-2,4,7-triene 5 suggest a tentative mechanism for thermal dimerization of cyclooctatetraene in which dimers 2, 3, and 4 are formed by coupling of the two isomers 5 and 6 of cyclooctatetraene.
Inositol Derivatives. V. Selective Benzoylation of 1,2-O-Cyclohexylidene-myo-inositol and Preparation of New O-p-Tolylsulfonyl-myo-inositols
Authors: Suami Tetsuo , Ogawa Seiichiro , Ohashi Kumiko , Oki Shuichi
Published: July 2006

The reaction of l,2-O-cyclohexylidene-myo-inositol (1a) with 1.5 equiv. of benzoyl chloride below 0°C gave 3-O-benzoate (2a) predominantly in 40% yield, together with easily separable 3,6-di-O-benzoate (3a) in 2.5% yield. Selective sulfonylation of 2a gave three new O-p-tolylsulfonyl-myo-inositols (the 4,6- (8a), 4,5- (9a), and 4,5,6-p-toluenesulfonates (10)). From 3a, two O-p-tolylsulfonyl derivatives (5- (15a) and 4,5-p-toluenesulfonates (16)) were obtained. The relative reactivities, toward benzoylation, of the hydroxyl groups of 1a were shown to be almost similar to those observed in tosylation. The p-tolylsulfonyloxy function on C–5 of 10 was found to be readily displaced preferentially by chloride ion.
Calculation of Optical Rotational Strength by Means of Various Types of Molecular Orbitals
Authors: Imamura Akira , Hirano Tsuneo , Nagata Chikayoshi , Tsuruta Teiji
Published: July 2006

The optical rotational strengths of the methyl derivatives of cyclohexanone were calculated by means of various types of molecular orbitals, which were converted from those used in the CNDO/2 method. One of them is represented as a Sla ter-basis atomic orbital transformed from molecular orbitals on a CNDO basis by using the overlap matrix. Another was obtained only by modifying the normalization coefficient of the molecular orbitals. From the results, the two-center matrix elements in the calculation of rotational strengths was found to be not negligible, hence, the above-mentioned transformation was indicated to be indispensable. Good agreement with the experimental results was found for the transformed molecular orbitals, especially for those with a modification of the normalization coefficient. The theoretical grounds for these transformations are discussed. The formulae for the matrix elements of the gradient operator which are necessary for the calculation of the rotational strength are given in the appendix.
Studies of Helical Aggregates of Molecules. III. The Bivalent Metal Soaps of Optically Active 12-Hydroxyoctadecanoic Acid
Authors: Tachibana Taro , Kayama Kazuko , Takeno Hideko
Published: July 2006

The bivalent metal soaps of optically-active 12-hydroxyoctadecanoic acid were found to crystallize out in the form of twisted fibers from aqueous or anhydrous ethanol solutions. Most soaps of this class produced both righthanded and left-handed fibers from the same specimen, more of the latter in the case of the D-enantiomer. An enantiomorphic relationship of the sense of twist was clearly demonstrated by using both enantiomers of the Ca soap. Under a high-resolution electron microscope, it was observed on the Sr soap that Sr atoms are arranged in lines along the fiber axis with a periodicity of 33–40 Å, showing that the hydroxyoctadecanoate chains of the soap molecules are aligned approximately parallel to the width of the fiber. The twisting of the soap fibers was associated with the layer structure characteristic of soap.
The Second CMC of the Aqueous Solution of Sodium Dodecyl Sulfate. I. Conductivity
Authors: Miura Masaji , Kodama Michiko
Published: July 2006

The conductivity studies of the aqueous solution of sodium dodecyl sulfate (SDS) over the concentration range of 0–0.12 m revealed that there exists a so-called 2nd critical micelle concentration (CMC) at about 65 mm in addition to the 1st CMC at 8.3 mm. The 2nd CMC was greatly influenced by additives; sodium chloride lowered the 2nd CMC, whereas organic substances, such as dodecyl alcohol and n-hexane, raised it. Moreover, the specific conductivity-concentration curve of the pure SDS solution broke upward at the 2nd CMC, and its slope increased in the presence of sodium chloride, while it bent toward the concentration axis in the presence of a certain amount of dodecyl alcohol or n-hexane. These facts may afford a clue for explaining the micelle structure above the 2nd CMC.
The Synthesis of Purine Nucleosides of l-Mycarose and l-Cladinose
Authors: Koto Shinkiti , Zen Shonosuke , Omura Satoshi , Hata Toju
Published: July 2006

Purine nucleosides of l-mycarose and l-cladinose, neutral branched-chain sugars of macrolide antibiotics, synthesized by a fusion method with the aid of dichloroacetic acid. The structure of these synthesized nucleosides was determined on the basis of the results of elemental analyses and the ultraviolet absorption and proton magnetic resonance spectra, as well as on the basis of the optical rotatory dispersion.
Studies on Stable Free Radicals. VII. The Mechanism for Cyclization Reaction of α-Amino Nitriles with Carbonyl Compounds
Authors: Toda Toshimasa , Morimura Syoji , Murayama Keisuke
Published: July 2006

Substituted 4-oxoimidazolidines were prepared by the condensation of α-amino nitriles with carbonyl compounds, or by the self-condensation of α-amino nitriles. The mechanism of the reaction was studied. The mass spectrum of the condensation product obtained by the reaction of cyclohexanone with 1-amino-1-cyano-15N-cyclohexane (III) or by the self-condensation of III, and the ESR spectrum of corresponding nitroxide radical obtained by the oxidation of the respective condensation products served to elucidate the reaction mechanisms for these condensation reactions. The mechanism for the self-condensation of α-amino nitriles proposed previously was corrected from the spectral data of the reaction product. Possible mechanisms for these condensation reactions are proposed.
Solvolysis of Organic Phosphates. V. Participation of the Neighboring Groups and Effects of Metal Ions in the Hydrolysis of 3-Hydroxy-2-pyridylmethyl Phosphate
Authors: Murakami Yukito , Sunamoto Junzo , Ishizu Hideyuki
Published: July 2006

The spontaneous hydrolysis of 3-hydroxy-2-pyridylmethyl phosphate was investigated at 60, 70, and 80°C over the–log[H+] range from 1 to 10 in aqueous media with an ionic strength of 0.10. The reactions followed apparent first-order kinetics with respect to the unreacted phosphate species, and the maximum rate was observed at–log[H+] 7–8. Reactive species in hydrolysis were neutral zwitterion, monoanion, and dianion species, the reactivity increasing in this order. This trend in reactivity order has not been observed previously. In a moderately acidic region (–log[H+]<2.0), kinetic data were consistent with the acid catalysis acting on the zwitterion species. Activation parameters provide an evidence for the unimolecular nature of the transition state in spontaneous hydrolysis and suggest the Al process for the acid catalyzed reaction. The anomalously high reactivity of the dianion species was attributed to participation of the 3-hydroxy group in the reaction process: intramolecular transfer of the hydroxyl proton to the ester oxygen in a pre-equilibrium stage, followed by the P-O bond cleavage in the subsequent transition state to give the products. Hydrolysis was also carried out in the presence of copper(II), nickel(II), zinc(II), aluminum (III), iron(III), and thorium(IV) ions at 60°C and μ=0.10 in a relatively lower pH range. Introduction of the 3-hydroxyl group to 2-pyridylmethyl phosphate resulted in a change of catalytic status of various metal ions. Only iron(III) and thorium(IV) ions accelerated the rate to a significant extent. Validity of the two requirements originally proposed for the bivalent metal catalysis was extended to the polyvalent metal catalysis.
Metal Catalysts Supported on Zeolite. I. A Study on Platinum Particles Distribution
Authors: Kubo Toshihiko , Arai Hiromichi , Tominaga Hiroo , Kunugi Taiseki
Published: July 2006

Zeolite 13Y, loaded with platinum cations by ion exchange, was calcined in the air and subsequently reduced in a hydrogen stream. Hydrogen and carbon monoxide adsorption studies, together with an electron microscopic observation of the catalyst, revealed that the size distribution of platinum particles is controlled by the calcination temperature. The hydrogen chemisorption method gave the average particle diameters, which were in fairly good agreement with the observations made by means of an electron microscope on the catalyst with a platinum particle diameter larger than 20 Å, while trace amounts of hydrogen chemisorption were observed for platinum particles less than 20 Å.
The Abnormal Absorption Intensity of the C-H Stretching Vibration Band in Chloroform Vapor. I. The CNDO Calculation Involving the 3d Orbitals
Authors: Miyazaki Tomoo , Shigetani Tsunehisa , Yamamoto Hiroshi
Published: July 2006

By the CNDO calculation involving the 3d orbitals, the infrared absorption intensity of the C–H stretching vibration band in chloroform vapor has been discussed in comparison with those of methyl chloride and methylene chloride. The value of the 3d orbital exponent of the chlorine atom was estimated on the basis of calculations using different values of the 3d orbital exponent on methyl chloride. The absolute intensities of the fundamental and the first overtone bands were calculated from the values of the first and the second derivatives of dipole moments with respect to the normal coordinates. From the results of these calculations, it follows that the electrical properties of the vibrating bond are the most effective factors in bringing about the abnormal absorption intensity of the C–H stretching vibration band in chloroform vapor.
Excimer and Monomer Defect Emissions of Perylene and Pyrene Crystals as Studied by the Nanosecond Time-resolved Spectroscopy Technique
Authors: Inoue Akinori , Yoshihara Keitaro , Kasuya Takahiro , Nagakura Saburo
Published: July 2006

Nanosecond time-resolved fluorescence spectra were measured at 77°K for pyrene and perylene crystals, and anomalous emissions which have lifetimes of ∼ 8 nsec and are difficult to be found by the usual steady excitation, were observed at the higher-wave number sides of the usual excimer emissions. From the band position and the vibrational structure, the anomalous emission was interpreted as being due to monomer defects in each crystal. The analysis of the observed rise and decay curves of the monomer defect and excimer emissions shows that the excited states of both emissions are populated independently from the band level of each crystal excited by light irradiation. The temperature dependence of the emission indicates that a thermal activation of 0.035 eV is required for the excimer formation in a perylene single crystal, while no activation energy is required for the excitation of the monomer defect.
Mordant Blue 31 as a New Fluorometric Reagent for Aluminum, Gallium, and Scandium
Authors: Hiraki Keiz\={o}
Published: July 2006

A sensitive fluorometric determination of aluminum, gallium, and scandium with Mordant Blue 31 was worked out. The reagent reacts with aluminum, gallium, scandium, yttrium, lanthanum, lutetium, indium, and magnesium in acidic or basic medium to form complexes with reddish yellow fluorescence. The complexes of aluminum (pH: 5–7), gallium (pH: 4), and scandium (pH: 6) exhibit strong fluorescence with an emission maximum at 590, 600, and 610 nm, respectively. The effects of time, pH and the concentration of the reagent were investigated. In acidic medium, aluminum, gallium, and scandium were found to form 1:1 complex with Mordant Blue 31. Under the optimum conditions, 0.1–3μg of aluminum, 1–12μg of gallium, and scandium in 25 ml sample solution could be determined. Although the fluorescence intensity of aluminum and gallium complexes was a little lower than that of the lumogallion complexes, Mordant Blue 31 was also applicable as a fluorometric reagent for aluminum and gallium. Since scandium-Mordant Blue 31 complex exhibits the strongest fluorescence of all other scandium-azo dye complexes, the reagent was used as a fluorometric reagent for scandium.
Oxovanadium(IV) Complexes of Schiff Bases Obtained from Salicylaldehyde Derivatives and Arylamines
Authors: Kuge Yoshio , Yamada Shoichiro
Published: July 2006

Oxovanadium(IV) complexes of Schiff bases obtained from salicylaldehyde derivatives and arylamines (abbreviated as VO(X-SAL.R)2) have been synthesized, where X=H, 5,6-benzo, 5-Cl, and 5-Br, and R=Ph, CH3-Ph, 2,6-(CH3)2-Ph and 2,6-(C2H5)2-Ph, Ph being phenyl nucleus. Complexes of the type VO(5-X-SAL.Ph)2 in the solid state, X being Cl and Br, consist of the species having a different configuration from that of the other complexes. For the latter complexes, distortion from the square-pyramidal configuration is not apparent in the solid state or in non-donor solvents, but in pyridine they combine with one pyridine molecule to form six-coordinate vanadium(IV) complexes. Comparison shows that the tendency toward the distortion in the solid state is lower with R=aryl than with R=α-branched alkyl groups.
Stereochemical Studies of Metal Chelates. VI. The Separation and Stereochemistry of Isomers of Dichloro((3S,8S)-dimethyl triethylenetetramine)cobalt(III) Perchlorate
Authors: Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

The cis-α and cis-β isomers of dichlorocobalt(III) complexes with (3S, 8S)-dimethyltriethylenetetramine were isolated. These isomers were stereospecifically formed in the Λ and Δ absolute configurations respectively. The cis-β isomerh as the Δ-β(RS) geometry, in which the configurations with respect to the coordinated secondary nitrogen centersof tetramine differ from one another. The difference between the Δ-β(RS) and Δ-β(RR) (and Λ-β(SS)) forms was noticed in the circular dichroism curves in the first absorption band region.
Synthetic Reactions by Complex Catalysts. XXV. The Copper-catalyzed Reaction of Allyl Isocyanide with Carbonyl Compounds and Olefins. Syntheses of 4-Vinyl-2-oxazoline and 5-Vinyl-1-pyrroline Derivatives
Authors: Saegusa Takeo , Murase Ichiki , Ito Yoshihiko
Published: July 2006

This paper describes two reactions of allyl isocyanide (AIC) by means of the Cu2O catalyst; these reactions produce heterocyclic compounds with vinyl substituents. First, the reactions of AIC with such carbonyl compounds as ketones and aldehydes produce 4-vinyl-2-oxazoline derivatives (1) in good yields. Second, AIC also reacts with the C=C double bond of α,β-unsaturated nitriles and esters to produce 5-vinyl-1-pyrroline derivatives (4,5, and 6). A mechanistic scheme involving an isocyanoallylcopper complex (11) has been assumed.
The Cope Rearrangement of Bridged Homotropilidenes Studied by MINDO Methods
Authors: Iwamura Hiizu , Morio Kazuhiko , Kunii Tosiyasu L
Published: July 2006

The theoretical structures and heats of formation of semibullvalene (1a), barbaralane (1b), and bullvalene (1c) have been investigated by the MINDO methods. The strain energies are estimated to be 19.7, 8.8, and 0.5 kcal/mol, respectively. The activation energies for the Cope rearrangement of these bridged homotropilidenes were obtained by a comparison of the results of a similar study on the biallylic transition states for the rearrangement. They are in good agreement with the experimental values. Extremely facile rearrangement in 1a is attributed to the partial release of strain energy through the formation of the transition state, and to the proximity (2.16 Å) of the non-bonded termini of the divinylcyclopropane unit in the ground state.
The Crystal Structure of 1-Ethyl-5-bromouracil. II. The Crystal Structure of the Form II Crystal of 1-Ethyl-5-bromouracil
Authors: Tsukihara Tomitake , Ashida Tamaichi , Kakudo Masao
Published: July 2006

Two crystalline forms of 1-ethyl-5-bromouracil were found. The crystal structure of the form II has been determined. The dimension of the tetragonal unit cell are a=b=17.13 Å, c=5.36 Å, and Z=8. The space group is P42⁄n. The final R is 0.064. The hydrogen bond scheme in this crystal, N(3)–H(3)···O(2), is the first finding in alkylated pyrimidine dimers. The carbon atom binding to the nitrogen atom of the pyrimidine ring deviates significantly from the pyrimidine ring plane.
Infrared Absorption Spectra of Aminobenzoic Acid Coordination Compounds
Authors: Inomata Tadaaki , Moriwaki Takao
Published: July 2006

Several divalent metal-aminobenzoic acid coordination compounds were prepared in aqueous solutions and their thermal analyses, magnetic moments, and infrared spectra were investigated. These coordination compounds have the structure of ML2 or ML2·nH2O and are coordinated with amino and carboxyl groups of the ligand. Metal-o-aminobenzoic acid chelates give approximately the same infrared spectra but metal-m- and p-aminobenzoic acid coordination compounds are classified into two groups by their infrared spectra. Detailed assignments for the infrared absorption bands of the metal-coordination compounds have been made by a comparison of the spectra with those of the ligand and its related compounds.
A Study of Silver(I) Complexes with Some π-Donors and n-Donors in Chloroform by the Solvent Extraction Method
Authors: Sekine Tatsuya , Takahashi Yoshihiro
Published: July 2006

The solvent extraction of silver(I) in a 0.1 M constant-ionic-strength solution into chloroform with 2-thenoyltrifluoroacetone(TTA) and with caproic acid was studied by means of radiometry. It was found that these extractions are enhanced by the addition of aliphatic and cyclic alkenes, of aromatic hydrocarbons, and of some n-donors. The enhancement of the extraction was explained in terms of the formation of molecular complexes of the silver(I)-TTA chelate or of silver(I) caproate in chloroform. By an analysis of the experimental data, the stability constant of the silver(I)-TTA chelate in the aqueous phase, and the stability constants of the molecular complexes in the chloroform phase with these donors, were determined. Some consideration was made of these results and of the possibility of the application of these extraction systems to analytical chemistry.
Arylation and Vinylation Reactions of Benzo[b]furan via Organopalladium Intermediates
Authors: Kasahara Akira , Izumi Taeko , Yodono Minoru , Saito Ryu-ichi , Takeda Toru , Sugawara Toshiaki
Published: July 2006

The Heck reaction of benzo[b]furan with arylpalladium chloride leads to the formation of 2-arylbenzo[b]-furan derivatives. In the presence of palladium acetate, benzo[b]furan reacts in benzene to give 2,2′-bibenzo[b]furyl, accompanied by 2-arylbenzo[b]furan. In the phenylation of [2-2H]benzo[b]furan with phenylpalladium salts, it was confirmed that no hydride shift takes place in the reaction. In the presence of palladium acetate, benzo[b]furan also reacts with olefin to produce benzo[b]furyl-substituted olefins, accompanied by a small amount of 2,2′-bibenzo[b]furyl, and from the reaction of [β,β-2H2]styrene and benzo[b]furan in the presence of palladium acetate it was confirmed that no hydride shift occurs in the reaction.
The Reduction of Triazolium and Tetrazolium Iodides with Sodium Borohydride
Authors: Isida Tyuzo , Akiyama Tetsuo , Mihara Nobutake , Kozima Sinpei , Sisido Keiiti
Published: July 2006

The sodium borohydride reduction of azolium iodides containing two, three, or four nitrogen atoms in the ring was studied. 1,4,5-Trisubstituted tetrazolium iodides gave Δ2-tetrazolines, whereas 1,3,5-trisubstituted tetrazolium iodide yielded no reduction product. 1,3,4,5-Tetrasubstituted 1,2,4-triazolium iodides and 1,2-disubstituted 1,2,3-triazolium fluorosulfonate were reduced to Δ2-1,2,4-triazolines and Δ2-1,2,3-triazoline respectively, but 1,3,4,5-tetrasubstituted 1,2,3-triazolium iodides were not reduced at all. Both pyrazolium and imidazolium salts gave the corresponding azolidines. These results can be explained in terms of the characteristics of sodium borohydride, which reduces selectively the immonium moiety in azolium salts.
The Optical and Electrical Properties of Metal Photodoped Chalcogenide Glasses
Authors: Shimizu Isamu , Sakuma Hiraku , Kokado Hiroshi , Inoue Eiichi
Published: July 2006

The optical and electrical properties of the metal photo-doped chalcogenide glasses were studied. The optical absorption of the chalcogenide glasses e.g., the As–S, As–S–Te, and As–S–Se systems) was increased by the photo-doping of such metals as Ag and Cu in the region of their absorption edges. The electrical conductivity of the glasses also increased with the photo-doping of the metals. The effective band gap obtained from the results of the temperature dependency of the electrical conductivity decreased with the increase in the amount of metal which was photo-doped in the glasses. The results obtained in this study suggest that the metals photo-doped in the chalcogenide glasses behaved as structural modifiers of the glasses, and that the state of density in the gap was increased by the metal photo-doping.
Thermal Decomposition Reactions of Metal Oxalato Complexes in the Solid State. II. Evolved Gas Analyses of Metal Oxalato Complexes
Authors: Nagase Kenzo
Published: July 2006

The thermal decomposition reactions of a number of metal oxalato complexes in the solid state were studied by an EGA method in a helium atmosphere. As regards the decomposition stage of an anhydrous complex, the complexes investigated could be divided into three groups: the complexes of Mn(III), Fe(III), Co(III), Rh(III), Cu(II), Pd(II), and Pt(II), this first group giving only CO2 as a gaseous product, decomposed by electron transfer from an oxalato ligand to a central metal ion; the complexes of Al(III) and Zn(II), this second group giving CO and CO2 in the molar ratio of 1:1, decomposed by C–O bond breaking to form a metal oxide with no change in the oxidation number of a central metal; and the complexes of V(III) and Cr(III), this third group giving CO2and a smaller amount of CO, decomposed through both the processes, electron transfer and C–O bond breaking. The subsequent decomposition reactions of the bivalent metal oxalato complexes formed upon heating the corresponding trivalent metal oxalato complexes were divided into two types: one is associated with further reduction of a central metal ion, while the other is associated with C–O bond breaking.
Binuclear Metal Complexes. VI. Syntheses and Properties of Binuclear Copper(II) Complexes of 2,6-Bis[N-(β-dialkylaminoethyl)iminomethyl]-4-methylphenol
Authors: Okawa Hisashi , Tokii Tadashi , Nonaka Yasuomi , Muto Yoneichiro , Kida Sigeo
Published: July 2006

A new series of binuclear copper(II) complexes, [Fsal(=NenNR2)2Cu2X]2+ (R=Me and Et, X=Cl, Br, and OH), were synthesized, where Fsal(=NenNR2)2 indicates the Schiff base prepared from 2,6-diformyl-4-methylphenol and N,N-dialkylethylenediamine (alkyl=methyl(Me) and ethyl(Et)). Two copper(II) ions are connected with the phenolic oxygen and X. The complexes obtained were characterized by elemental analyses, infrared and visible spectra, molar conductivities in methanol, ESR spectra and magnetic susceptibilities. It was found that the stability of the complexes decreases in the order X=OH>>Br>Cl. It was concluded from cryomagnetic measurements that the effect of the bridging group X on spin-coupling decreases in the order OH>>Br>Cl.