bluuebunny/crossref_metadata_2025 huggingface dataset:
The Magneto-Optical Rotatory Dispersion of Benzophenone in the S0→T (n-π*) and the S0→S1 (n-π*) Absorption Regions
Authors: Takenoshita Yoshiya , Kanda Yoshiya
Published: July 2006

The magneto-optical rotatory dispersion (MORD) of benzophenone has been measured in the spectral regions corresponding to its S0→S1(n–π*) and S0→T(n–π*) absorption systems. The abnormal MORD in the S0→T absorption region has not always been observed, contrary to the results by Shashoua, only the normal MORD has always been observed. The MORD in the S0→S1(n–π*) absorption region changes its sign at about 340 mμ and is classified as a positive (B+C/kT) type, according to Stephens et al. It has been concluded that the MORD of the S0→S1 transition of benzophenone occurs as a result of the n,π* state, S1 being mixed with the B2u-analogue state, S3, and that then the S1 state interacts magnetically with the S3 under an external magnetic field.
Linear Antiferromagnetic Interaction in Organic Free Radicals
Authors: Yamauchi Jun
Published: July 2006

The static magnetic susceptibilities from 1.8°K to 300°K, and the ESR spectra from 1.5°K to 300°K, of several organic free radicals have been measured on powder samples. The broad maxima in the susceptibility which indicate the antiferromagnetic interaction and the broadening of the ESR absorption lines have been observed. The data are analysed on the basis of the linear Heisenberg model and shown to be consistent with the one-dimensional magnetic chain model of isotropic exchange interaction. Discussions are made of the grounds of susceptibility, the ESR, and the specific heat measurements. In addition to a short-range ordering of spins, the possibility of long-range ordering is also discussed in two radicals, BDPA-Bz and p-Cl-BDPA, on the basis of discontinuities in the slope of susceptibility, the rapid broadening of the ESR linewidth, and the disappearance of the ESR absorption.
A New Phosphorylating Reagent. III. Preparation of Mixed Diesters of Phosphoric Acid by the Use of an Activatable Protecting Group
Authors: Mushika Yoshitaka , Hata Tsujiaki , Mukaiyama Teruaki
Published: July 2006

A novel method for the preparation of mixed diesters of phosphoric acid has been investigated. It was found that mixed diesters of phosphoric acid were prepared by the reaction of alkyl 2-chloromethyl-4-nitrophenyl hydrogen phosphates with alcohols in dry pyridine. On the other hand, these diesters were also obtained from dialkyl 2-chloromethyl-4-nitrophenyl phosphates on hydrolysis under mild conditions. By using both of these methods, analytically pure samples of mixed diesters of phosphoric acid could be obtained in high yields.
An Investigation of the Decomposition of the Intermediate Ions Produced by Electron Impact. I. C7H7+ Ions from Several Substituted Toluenes
Authors: Tajima Susumu , Niwa Yoshio , Nakajima Masahiko , Tsuchiya Toshikazu
Published: July 2006

The decomposition of the C7H7+ ions produced by electron impact from toluene, o-, m-, p-xylene, o-, m-, p-chlorotoluene, o-, m-, p-methylbenzoic acid, p-nitrotoluene, and p-methylacetophenone has been investigated. By the determination of the relative abundances of normal and metastable ions, these C7H7+ ions are shown to be identical in structure, except for the C7H7+ ion from p-nitrotoluene. The relative rates of decomposition of these ions are compared in terms of the relative abundances of the ions 65+/91+ (=R) and 46.5*/91+ (=R*) (where 46.5* is the abundance of the metastable ion for the 91+→65++26 decomposition; 91+ and 65+ denote the abundance of ions at m⁄e 91 and 65 respectively). Further, using the internal energy, the relative rates are estimated by comparing their R and R* values with the IRE curve i.e., R and R*  versus the bombarding electron energy) for p-methylacetophenone (PMAP), which was used as the standard compound.
Microwave Spectrum, Barrier Height to Internal Rotation of Methyl Group, and Dipole Moment of 3-Methylfuran
Authors: Ogata Teruhiko , Kozima Kunio
Published: July 2006

The microwave spectrum of 3-methylfuran was measured in the frequency region from 8.2 to 30 GHz. By observing the A-E splittings due to the hindering rotation of the methyl group, the barrier height was determined to be 1.09kcal/mol. The value is nearly the same as that of 2-methylfuran. The dipole moment was determined to be 1.03 D, which is a little larger than that of furan.
Synthesis and Elimination Reaction of O-Methyl Derivatives of Methyl (Methyl α-d-Glucopyranosido)uronate
Authors: Hashimoto Hironobu , Sekiyama Takeshi , Sakai Hideo , Yoshimura Juji
Published: July 2006

Several methyl ethers [2,3,4-tri-O-methyl- (1), 4-O-methyl- (2), 3-O-methyl- (3), and 2-O-methyl- (4)] of methyl (methyl α-d-glucopyranosido)uronate were used as model compounds for the examination of β-elimination reaction. 1 was purely synthesized from methyl α-d-glucopyranoside and both 3 and 4 were newly synthesized via the corresponding methyl ethers of methyl α-d-glucopyranoside. The condition of β-elimination reaction was examined using 1 as a model compound. It was shown that β-elimination reaction occurred only when an alkoxide was used as a base. The yield of the unsaturated product, i. e., methyl (methyl 4-deoxy-2,3-di-O-methyl-β-l-threo-hex-4-enopyranosido)uronate (13) was about 40–50% by sodium methoxide in methanol at 60–70°C, and 70–80% by potassium t-butoxide in t-butyl alcohol even at room temperature. In both cases the reaction was completed within several minutes. The β-elimination reaction was followed by UV spectra using the molecular extinction coefficient of purely isolated 13, and the reaction products were examined by gas-liquid chromatography. The β-elimination product of 2 was also obtained in good yield, but that of 3 in very poor yield.
Structures of Norbornane and Norbornadiene as Determined by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo
Published: July 2006

The structures of norbornane and norbornadiene in the gas phase have been investigated by electron diffraction. For the most probable models the rg bond lengths and the bond angles (based on the rα structure) with estimated limits of error are as follows: For norbornadiene: C1–C2=1.5354±0.007 Å, C2=C3=1.3432±0.003 Å, C1–C7=1.573±0.014 Å, ∠C1–C7–C4=94·1±3·0°, and θ (the dihedral angle between the C1–C2–C3–C4 and C4–C5–C6–C1 planes)=115·6±2·2°; For norbornane: C–C(average)=1.5488±0.003 Å, C1–C2=1.539±0.012 Å, C2–C3=1.557±0.025 Å, C1–C7=1.560±0.024 Å, ∠C1–C7–C4=93·1±1·7°, and θ=113·1±1·8°. The frame structures of these molecules are similar to each other except for the C2–C3 bond distances. All the C–C–C valence angles are appreciably smaller than the tetrahedral angle (∠C1–C7–C4 in particular). The C1–C7, bridge bonds appear to be longer than the normal C–C single bond. The above structures are compared critically with those reported so far by other investigators. A method for estimation of systematic errors in the structural parameters derived from a least-squares analysis with fixed mean vibrational amplitudes is discussed.
The Relation between the Volatilization Rates of Chlorine and Bromine Compounds from Volcanic Rocks on Heating
Authors: Takahashi Kazuyoshi
Published: July 2006

Experiments on the volatilization rate of chlorine and bromine compounds from volcanic rocks were made at temperatures above 770°C in a stream of nitrogen, both in the presence of water vapor and without it. The rate of volatilization have been studied by following the change in the retained chlorine and bromine contents as a function of the heating time. Their contents retained in rocks during heating were estimated indirectly by determining their amounts evolved from rocks. The chlorine compounds are more volatile than those of bromine, regardless of the rock type. However, the difference in their volatility becomes quite small in the presence of water vapor. This fact suggests that there is little difference in the volatility between chlorine and bromine compounds in the presence of much water vapor, so the Br/Cl ratio in magma does not change very much during the crystallization process.
The Crystal Structure of Perchlorato-bis(2,2′-bipyridine)copper(II) Perchlorate, [Cu(ClO4)(bipy)2]ClO4
Authors: Nakai Hisayoshi
Published: July 2006

The structure of bis(2,2′-bipyridine)copper(II) perchlorate, Cu(bipy)2(ClO4)2, has been determined from three-dimensional X-ray data collected by the photographic method. The compound forms triclinic crystals with a=7.44(1), b=14.93(1), c=15.32(1) Å, α=136.3(0.1), β=103.7(0.1), γ=83.2(0.1)°, and Z=2 in the space group P\bar1. The structure was solved by the usual Patterson and Fourier techniques and was refined by the least-squares method to an R value of 0.134. The crystal is composed of an infinite chain of [Cu(ClO4)(bipy)2+]∞ and ClO4−; a perchlorate ion in the chain bridges two adjacent copper atoms through its two oxygen atoms. Roughly speaking, the coordination polyhedron around the copper atom is a tetragonally-distorted octahedron; the four nitrogen atoms of bipyridine molecules are arranged in a flattened tetrahedral manner (average Cu–N=1.99 Å), the least-squares plane of these atoms making an equatorial plane, while the polar positions are occupied by the two oxygen atoms of perchlorate anions, the Cu–O distances being 2.45 and 2.73 Å. The two pyridine rings are twisted slightly to each other in both of the bipyridine molecules; the dihedral angle between the pyridine planes is 13° in one bipyridine ligand and 4° in the other.
The Preparation and Absorption Spectra of the Geometrical Isomers of Carbonatoglycinatodiamminecobalt(III)
Authors: Kanazawa Shuji , Shibata Muraji
Published: July 2006

Three geometrical isomers of the [CoCO3(gly)(NH3)2] complex, the mer(cis-diammine)-, mer(trans-diammine)-, and fac-isomers, have been isolated from a reaction mixture of the cis-[Co(CO3)2(NH3)2]− ion with glycine by means of a study of the solubility difference and by means of ion-exchange chromatography. These isomers have been characterized by the absorption spectra, the PMR spectra, and the infrared spectra. The absorption spectrum of the mer(trans)-isomer is of special interest, and there is a clear shoulder in the second absorption band region which may be due to the splitting of the second band.
The Synergic Solvent Extraction of Rare Earths. II. The Absorption Spectra of Neodymium-, Holmium-, and Erbium-TTA-TOPO Complexes with ClO4−, CNS− , NO3−, and Cl− Ions
Authors: Taketatsu Tomitsugu , Ohkura Nobuyo
Published: July 2006

The synergic solvent extraction behavior of neodymium, holmium, and erbium in Ln3+/X−/HTTA/TOPO systems (X−=ClO4−, CNS−, NO3−, and Cl−) have been investigated. When the rare earths are completely extracted into an organic layer, the following equation is assumed:

Ln(TTA)3(TOPO)2(0)+3TOPO(0)+H(a)++X(a)−\ightleftharpoons(Ln(TTA)2(TOPO)5)+X(0)−+HTTA(0)

for which the mixed equilibrium constant is defined by k3=[(Ln(TTA)2(TOPO)5)+X−](0) [HTTA](0)/[Ln(TTA)3-(TOPO)2](0)[TOPO]3(0) [H+](a)[X−](a). The logk3 value for the holmium/ClO4−, /CNS−, /NO3−, and /Cl− systems are about 8.3, 6.5, 5.3, and 3.6 respectively. An obvious difference between Ln3+/SO42−/HTTA/TOPO and Ln3+/ClO4−/HTTA/TOPO systems is observed in the order of the distribution ratio on the extraction of a series of rare earths with an increase in the atomic number.
Effect of Ring Size on the Acid-Catalyzed Reduction of Cyclic Sulfoxides by Iodide Ion
Authors: Tamagaki Seizo , Mizuno Masao , Yoshida Hiroshi , Hirota Hiroo , Oae Shigeru
Published: July 2006

Acid-catalyzed reduction of various cyclic sulfoxides with iodide ion were kinetically investigated. The rates of reduction of thianthrene, phenoxathiin, dibenzothiophene oxides were found to be in a linear relation with their basicities, while those of alicyclic sulfoxides fall in the following sequence with a 700 fold range; 5->4->open>7->6- membered cyclic sulfoxides. This rate sequence seems to be correlated better by the steric effect than by basicity difference. For further information on the possible effect of steric hindrance, a few methyl alkyl sulfoxides were also subjected to the same reaction, but the results could not be explained by steric effect only.
Di- and Trimethylenebis(ethylphenacyl)sulfonium Ylides
Authors: Kato Shinzi , Ishihara Hideharu , Mizuta Masateru , Hirabayashi Yoshio
Published: July 2006

Bissulfonium phenacylides were obtained by the reactions of dimethylene and trimethylene bisethylphenacylsulfonium salts with sodium hydride. The chemical properties of these bis-ylides are similar to those of monosulfonium phenacylides. Biscarbamoylsulfonium phenacylides were obtained as stable crystals by the reactions of the above bis-ylides with phenyl isocyanate.
Reactions of Metal Alkyl-Active Methylene Chelate Compounds with α,β-Unsaturated Carbonyl Compounds
Authors: Kawakami Yusuke , Tsuruta Teiji
Published: July 2006

The method of the preparation of zinc (or aluminum) alkyl-active methylene chelate compounds was studied. The chelate compounds were identified mainly by NMR, IR, and component analysis. Zinc alkyl-active methylene chelate compounds were found to cause a Michael-type addition reaction with α,β-unsaturated esters or nitriles. Aluminum alkyl-active methylene chelate compounds exhibited lower reactivities than the zinc chelate compounds toward α,β-unsaturated carbonyl compounds. Kinetic studies of the addition reaction revealed that the reaction proceeded according to a first-order rate law with respect to both the metal compound and the α,β-unsaturated carbonyl compound. The effects of substituents on the metal atom as well as on the chelate ring were also studied. The intercorrelation among the chemical shift of the methine proton of the chelate ring, σp of the subsituents and the reactivity of metal alkyl-active methylene chelate compounds suggested that the rate of the addition reaction was governed mainly by the stability of the chelate ring.
The Acid-catalyzed Reaction of Isocyanide with Oxetane
Authors: Saegusa Takeo , Taka-ishi Naotake , Ito Yoshihiko
Published: July 2006

The reaction of isocyanide with oxetane in the presence of BF3·OEt2 was studied; in this reaction a 1:1 cyclic adduct, 2-iminotetrahydrofuran, was formed. From 2-methyloxetane, 2-imino-5-methyltetrahydrofuran was exclusively formed. These findings suggest an SN2 mechanism for the cleavage of the oxetane ring. Oxetanes with electron-withdrawing substituents gave γ-alkoxybutyronitrile as the main product, along with 2-iminotetrahydrofuran. A reaction scheme involving an imidoyl cation was proposed to explain the formation of cyclic and linear products.
Photocycloaddition of Thiocarbonyl Compounds to Multiple Bonds. VII. The Reaction of Thiobenzophenone with Acetylenic Compounds
Authors: Ohno Atsuyoshi , Koizumi Tamotsu , Ohnishi Yutaka
Published: July 2006

Photocycloaddition of thiobenzophenone to acetylenic compounds, R–C≡C–R′ (R=COOH, Ph, CH2OH, and CN; R′=H: R=COOMe; R′=COOMe), affords 1-phenyl-2-thia-1,2-dihydronaphthalene derivatives. The key step to the product is an intra-molecular aromatic substitution of the composite vinylic biradical 13. The difference in reactivity of acetylenic and olefinic compounds as well as that between thiobenzophenone and benzophenone are discussed. Ethoxyacetylene does not undergo the reaction. This is interpreted in terms of electronegativity of a radical center in 13. It is found that cyanoacetylene reacts with butanethiyl radical in contrast to its olefin analog, acrylonitrile.
Selective Cleavage of Cysteine Peptides
Authors: Inui Toshishige
Published: July 2006

The cysteine peptides such as IV were cyclized to thiazolidone peptides through the corresponding S-chlorocarbonyl derivatives. In some peptides such as XXII, however, no cyclized products were isolated because of decomposition of the S-chlorocarbonyl intermediates. By the mild alkaline hydrolysis of the thiazolidone peptide the carboxylic acid from the N-terminal amino acid or peptide and 2-oxothiazolidine-4-carbonyl derivatives were isolated as a result of the selective cleavage of the peptide bond in which an amino group of cysteine residue participated. This cleavage reaction was applied to several cysteine peptides. The same results were observed whenever the corresponding thiazolidone peptides were formed.
Studies on Aminosugars. XXVII. Synthesis of Several Glycosides Containing (6-Amino-6-deoxy-d-glucopyranosyl)-2-deoxystreptamine
Authors: Nishimura Yoshio , Tsuchiya Tsutomu , Umezawa Sumio
Published: July 2006

Racemic O-isopropylidene derivative of N,N′-diethoxycarbonyl-2-deoxystreptamine was glycosidized with 6-azido-2,3,4-tri-O-benzyl-6-deoxy-α-d-glucopyranosyl chloride to afford two kinds of positional isomers of α-glucoside, which led to 4-O-(6-amino-6-deoxy-α-d-glucopyranosyl)- and 6-O-(6-amino-6-deoxy-α-d-glucopyranosyl)-2-deoxystreptamine. In a similar manner, 4-O-(6-amino-6-deoxy-α and β-d-glucopyranosyl)-6-O-(α-d-glucopyranosyl)-2-deoxystreptamines and 4-O-(6-amino-6-deoxy-α and β-d-glucopyranosyl)-6-O-(6-amino-6-deoxy-α-d-glucopyranosyl)-2-deoxystreptamines were synthesized.
Studies on Aminosugars. XXVIII. Synthesis of β-l-Idopyranosides through the Corresponding 5-Enopyranosides
Authors: Ikeda Daishiro , Tsuchiya Tsutomu , Umezawa Sumio
Published: July 2006

Methyl 6-deoxy-β-l-idopyranoside (7), methyl 2-amino-2,6-dideoxy-β-l-idopyranoside (13) and methyl 3-amino-3,6-dideoxy-β-l-idopyranoside (28) have been prepared through the corresponding suitably protected 5-enopyranoside precursors in good yields.
Intramolecular Fluorescence Quenching Effect by p-Nitrophenyl and p-Nitrophenoxy Groups
Authors: Mutai Kiyoshi
Published: July 2006

The intramolecular fluorescence quenching efficiency of p-nitrophenyl and p-nitrophenoxy groups in homologous series of p-O2NC6H4(CH2)nNH-1-Naphthyl (I, n=1–7) and p-O2NC6H4O(CH2)nNH-1-Naphthyl (II, n=2–6), respectively, has been determined. The quenching effect is observed even in the highest homologs of both series. From the fact that the fluorescence intensity of n=2 homolog of I is higher than that of n=1, together with spectroscopic data it is concluded that the higher intensity of n=2 than n=1 of the across-space intramolecular charge-transfer band is due to the larger absorbance per interacting molecule of n=2, the origin of which might be attributed to the different interacting conformations of these homologs. The effect of the number of methylene groups (n) on the fluorescence spectral shape has also been found.
An MO Interpretation of the Chemical Shifts of Inner-shell Electrons
Authors: Kato Hiroshi , Ishida Kazuhiro A , Nakatsuji Hiroshi , Yonezawa Teijiro
Published: July 2006

A correlation formula between the chemical shifts of inner-shell electrons and molecular-charge distributions is derived by an MO scheme with CNDO-type approximations. Errors imposed in these schemes are discussed. Reorganization energy terms are briefly discussed in the same level of approximations.
The Estimation of the Surface Properties of Metal Oxides by the Use of TCNQ Adsorption
Authors: Hosaka Hiroshi , Fujiwara Takao , Meguro Kenjiro
Published: July 2006

The electron-donor properties of metal oxides (magnesia, alumina, silica, titania, zinc oxide, and nickel oxide) were investigated by means of TCNQ adsorption. When TCNQ was adsorbed on the surfaces of the metal oxides from its acetonitrile solution, the surfaces of the metal oxides acquired the colorations characteristic of each oxide. The coloration was caused by the formation of TCNQ anion radicals on the metal oxide surfaces. The presence of the TCNQ anion radicals on the colored metal oxide surfaces was confirmed by studying the ESR absorption and electronic spectra. The radicals were formed as a result of electron transfer to TCNQ from the metal oxide surfaces. The order of the radical-forming activity, determined by ESR, was as follows: magnesia>zinc oxide>alumina>titania>silica>nickel oxide. The electron-donor property of the metal oxide surfaces might be dependent on the natures of the semiconductor and the surface hydroxyl ion.
Effect of Phase on Hot Hydrogen Atom Abstraction Reaction with Solid Isobutane as Studied by Electron Spin Resonance Spectroscopy
Authors: Wakayama Terunobu , Miyazaki Tetsuo , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

The effect of phase on the hot-hydrogen-atom abstraction reaction with isobutane at 77°K has been studied by electron spin resonance spectroscopy in the photolysis and the radiolysis of solid isobutane containing hydrogen iodide. While only the isobutyl radical is formed by the UV-illumination of isobutane–hydrogen iodide systems in the polycrystalline state, the tertiary butyl radical, accompanied with a small amount of isobutyl radicals, is produced from isobutane-methylcyclohexane-hydrogen iodide systems in the glassy state. The hot hydrogen atom produced by dissociative electron attachment to hydrogen iodide abstracts the tertiary hydrogen atom from isobutane at 77°K, independent of whether the matrix is polycrystalline or glassy. It appears that the H-abstraction reaction from isobutane by hot hydrogen atoms depends upon the energy of the hot hydrogen atoms.
A New Method of Solubility Determination of Hydrolyzing Solute—Solubility of Benzyl Chloride in Water
Authors: Ohnishi Ryuichiro , Tanabe Kozo
Published: July 2006

A method of determining the solubility of a solute with a considerable rate of hydrolysis and small solubility in water was devised. The method consists of measurements of the hydrolysis rate below or at saturation solubility, the rate constants and order of reaction, and analysis of kinetic data. The solubility of benzyl chloride in water was found to be 33.1 mg/100 ml at 4.5°C, 49.3 at 20°C, and 55.5 at 30°C. Solubility of benzal chloride and benzotrichloride was calculated to be 25 mg/100 ml at 30°C and 5.3 at 5°C, respectively, by utilizing the kinetic data given in literature
The Crystal Structure of Ascochlorin p-Bromobenzenesulfonate
Authors: Nawata Yoshiharu , Iitaka Yoichi
Published: July 2006

The structure of ascochlorin, C23H29O4Cl, has been determined by the three-dimensional X-ray crystal structure analysis of ascochlorin p-bromobenzenesulfonate. The crystal is orthorhombic, space group P212123, with four molecules in a unit cell of dimensions, a=13.86, b=30.04, and c=6.82 Å. The structure was solved by the heavy atom method and refined by the method of block-matrix least-squares. The final R value was 0.102 for 1627 independent reflexions. Ascochlorin consists of (3-chloro) orcylic aldehyde and (2,3,4-trimethyl) cyclohexanone moieties which are connected with each other through a zigzag chain of trans-(3-methyl)penta(2,4)diene. The cyclohexanone ring takes a typical chair form, and the intramolecular hydrogen bond exists in the orcylic aldehyde residue. The absolute configuration was determined by the anomalous dispersion method.
Electrochemiluminescence of Aromatics in N,N-Dimethylformamide
Authors: Mori Kenji , Yamamoto Naoto , Tsubomura Hiroshi
Published: July 2006

Electrochemiluminescence (ECL) of aromatics was studied in dimethylformamide. The solutions were electrolyzed with square-wave voltage at various frequencies. For anthracene, emission from species produced by electrochemical reaction was observed together with anthracene fluorescence. These emissions were quenched when water was added to the solution. For rubrene and perylene, fluorescence from the molecules was observed. For phenanthrene, emission differing from phenanthrene fluorescence was observed at 515 mμ.
The Crystal Structure of 3-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)-1-ethy1-2-methylpyrrolidine Hydrobromide
Authors: Tokuma Yoji , Nojima Hiroshi , Morimoto Yukiyoshi
Published: July 2006

The crystal structure of 3-(10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene)-1-ethyl-2-methllpyrrolidine hydrobromide, C22H26NBr, has been determined. The crystal is monoclinic with space group P21⁄a; the unit-cell dimensions are: a=30.16, b=18.78, c=7.048 Å, β=90.53°. The asymmetric unit contains two molecules. The intensities were estimated visually from the multiple-film equi-inclination Weissenberg photographs. The structure was solved by the heavy atom method. The atomic parameters were refined by the blockdiagonal least-squares method, and final R index was reduced to 0.147. It is concluded that the overall geometry of the two independent molecules is similar in every detail The pyrrolidine ring is puckered. The 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ylidene part consists of three planes. The dihedral angles between the planes are 63° for the benzene planes I and II, 59° for the benzene plane I and the ylidene plane, and 76° for the benzene plane II and the ylidene plane.
The Chelating Behavior of 1-(2-Phosphonophenylazo)-2-hydroxynaphthalene-3,6-disulfonic Acid with Alkaline Earth Metals
Authors: Kina Kenyu , Miyata Haruo , Tôei Kyoji
Published: July 2006

A new chelating agent, o-phosphonophenylazo-2-hydroxynaphthalene-3,6-disulfonic acid, has been synthesized. The acid dissociation constants of this ligand and the chelate stability constants with alkaline earth metals have been measured by the pH titration method at an ionic strengh of 0.10 and at 25.0±0.1°C. This ligand forms the acido complex, MHL, in the pH 5–7 region. The stability constants of the acido complex decrease in this order: log KSrHL≈logKCaHL>log KMgHL; whereas the decreasing order of the stability constants, logKML, is as follows: log KMgL>log KCaL>log KSrL.
The Stability of Fused Rings in Metal Chelates. VIII. Solution Equilibria of the Copper(II) Complexes of Glycinamide and Related Compounds
Authors: Yamaughi Osamu , Miyata Hiroko , Nakahara Akitsugu
Published: July 2006

The aqueous solution equilibria of the systems containing copper(II) ion and glycinamide, β-alaninamide, glycine-N,N-diethylamide, or β-alanine-N,N-diethylamide have been investigated by potentiometric titration at 25°C (μ=0.1 (KNO3)). The stability constants K1 and K2 and the constants of the deprotonation reactions K1H, Kc1, and Kc2, for the glycinamide-copper(II) systems, and K1 and K2 for the other ligand-copper(II) systerrs were calculated by the method of non-linear least-squares with the aid of a computer. The K1 values were found to be in the order, glycine-N,N-diethylamide (6.17)>β-alanine-N,N-diethylamide (5.5)>glycinamide (5.30)>β-alaninamide (5.1). The sequence reveals that the five-membered chelates are more stable than the six-membered ones. The K1 and Kc1 values for glycylglycine and β-alanylglycine have been determined anew, and the structures of the chelates formed in acid solution have been discussed from comparative studies of the equilibrium constants, which suggest a tridentate nature of the dipeptides in the chelates of the type Cu(HL)+ where HL denotes free dipeptide.
The Crystal Structure of (+)589-Dicyanobis(ethylenediamine)cobalt(III) Chloride Monohydrate
Authors: Matsumoto Keiji , Ooi Shun’ichiro , Kuroya Hisao
Published: July 2006

The crystal structure of (+)589-[Co(CN)2en2]Cl·H2O has been determined from three-dimensional X-ray photographic data. The crystals are monoclinic, with the lattice constants of a=8.15(1), b=11.69(2), c=6.61(1) Å, and β=107.1(2)°, and with the space group of P21 containing two formula units in the cell. The structure was solved by a conventional Fourier technique and was refined by the least-squares method to an R factor of 0.114. The absolute configuration of the complex ion can be denoted as Λ(λλ); this is in accordance with the assignment made by Mason et al. The complex ion has an approximately two-fold axis, and both of the ethylenediamine chelate rings are of the ob-conformation.
The Polymerization of Silacyclopentene and -pentane Derivatives
Authors: Araki Tsunao , Terunuma Daiyo , Sato Tamio , Nagai Norio , Furuichi Mitsuharu , Nakamura Shigeyoshi
Published: July 2006

The polymerization of 1,1,3-trimethyl-1-silacyclopentene-3 (I), 1-methyl-, 1-allyl-1,1-diallyl-1-silacyclopentenes and -pentanes with aluminum chloride was carried out. By means of an IR spectroscopic analysis of the resulting polymers, it was established that not only ring opening but also vinyl polymerization due to the C–C double bond occur in this polymerization. Attempts to polymerize I with other catalysts, such as BF3·OEt2, AIBN, KOH, and a Ziegler catalyst, were unsuccessful.
p-Nitrophenyl Phosphates as Phosphoryiating Reagents of Alcohols
Authors: Chong Kyu-Jang , Hata Tsujiaki
Published: July 2006

Phosphorylation of alcohols by means of P1,P2-di-p-nitrophenyl pyrophosphate and p-nitrophenyl phosphate was investigated. Alcohols were phosphorylated in almost quantitative yields by use of P1,P2-di-p-nitrophenyl pyrophosphate. It was found that p-nitrophenyl phosphate acts as an effective phosphorylating reagent for alcohols in dry pyridine to give the corresponding alkyl phosphate.
Chemically Induced Dynamic Nuclear Polarization in the Photochemical Reaction of Phenanthraquinone with Hydrogen Donors. I. Kinetics of Nuclear Spin Polarization
Authors: Maruyama Kazuhiro , Shindo Heisaburo , Otsuki Tetsuo , Maruyama Tetsuo
Published: July 2006

Strongly-enhanced NMR signals were observed in the photo-induced hydrogen abstraction reaction of phenanthraquinone with several hydrogen donors in benzene. Chemically-induced dynamic nuclear polarization was kinetically treated in the photochemical reaction during the course of irradiation by visible light and shut-off. It was found that the relaxation time of the nuclear-spin system under the irradiation is shorter by a factor of 2 to 4 than that in the black-out stage and that the enhancement factor for the methine proton of the 1,2-adduct of phenanthraquinone was evaluated as 1000–2000.
The Solvent Effect on the Reaction Selectivity in the Chlorination of Propionic Acid
Authors: Nagai Toshikazu , Horikawa Yukio , Ryang Hon Son , Tokura Niichiro
Published: July 2006

The chlorinations of propionic acid with chlorine were carried out at 70°C in various solvent mixtures with photo-irradiation or with initiation by benzoyl peroxide. Benzene - CCl4, naphthalene - CCl4, and anthracene -CCl4 mixtures, and sulfur dioxide - CCl4 were used as the solvents. In the benzene - CCl4 mixtures, the relative reactivity, β/α, of the a and the α positions of propionic acid changed from 1.68 (CCl4) to 1.11 (benzene), the ratio being inversely proportional to the electron-donor properties of the solvents. In the naphthalene -CCl4 mixtures, the plot of the relative reactivity, β/α, versus the naphthalene content showed a minimun at ca. 0.1 mol/l of naphthalene; however, the total yield of the chlorinated acids decreased as the content of the naphthalene increased. No chlorinated acids were obtained in the anthracene - CCl4 system. In the presence of sulfur dioxide, the α-position was more readily substituted than the β-position, the β/α ratio decreasing as the molar ratios of C12/SO2 were decreased, from 1.3 (Cl2/SO2=0.286/0.036) to 0.49 (0.286/0.858), by the initiation of benzoyl peroxide. However, dilution with CCl4 or photo-irradiated chlorination cause no change in the selectivity in spite of the presence of sulfur dioxide. A mechanism to account for such a selectivity has been suggested.
Solvent Effect in a Partial Asymmetric Synthesis. III
Authors: Nishiyama Kazuyoshi , Inouye Yuzo
Published: July 2006

The solvent polarity-dependence of asymmetric stereochemistry was unambiguously corroborated in the Michael type cyclopropane formation in a system designed so as to proceed through the transition state conformations of an equal dipole moment not involving any geometrical isomerism: the NaH-catalyzed condensation of (−)-menthyl methacrylate with ethyl chloromalonate in solvent media of varying polarity resulted in the formation of (−)-1-methylcyclopropane-1,2,2-tricarboxylic acid having the same sign of rotation in all cases. The fit of the stereochemistry to the Kirkwood equation was borne out by the linearity found for the plots of logR⁄S against the Kirkwood-Onsager parameter. The R-configuration of (−)-1-methylcyclopropane-1,2,2-tricarboxylic acid was established by the correlation to (+)-2,2-diphenyl-1-methylcyclopropanecarboxylic acid of the well-defined (R)-configuration.
The Crystal and Molecular Structure of N-Salicylidene-α-aminoisobutyratoaquocopper(II)
Authors: Fujimaki Hiroto , Oonishi Isao , Muto Fumio , Nakahara Akitsugu , Komiyama Yoshimichi
Published: July 2006

The crystal structure of N-salicylidene-α-aminoisobutyratoaquocopper(II), [Cu{OOCC(CH3)2N=CHC6H4O}(H2O)], has been determined from the three-dimensional X-ray diffraction data. The crystals are monoclinic. The cell dimensions are: a=12.30, b=8.45, c=23.84 Å, and β=91.0°. The space group is P21/c, with eight formula units in a unit cell. The structure has been refined by the least-squares method, with anisotropic temperature factors, to an R-value of 0.10. The molecular structures of the complex are essentially the same as those of N-salicyl ideneglycinatoaquocopper(II) hemihydrate and tetrahydrate. The environments of the copper(II) ions are square pyramidal, with one long and four short coordination bonds. The average distances of the two copper environments are: Cu–O, 1.912 and 1.945; Cu–N, 1.961; Cu–O(H2O), 1.989, and Cu–O′ (the bond to the carboxyl oxygen of the adjacent molecule), 2.344 Å. The average bond distances of N=C in the salicylaldimine residue and of N–C in the α-aminoisobutyrate group are 1.271 and 1.504 Å respectively. Neighboring molecules related by a center of symmetry are linked together alternately by hydrogen bonds and coordination bonds (Cu–O′), an infinite chain being formed along the b-axis. However, there are no interactions other than van der Waals forces along the a- and c-axes.
Synthesis of cyclo-Diglycyl-l-tyrosyl-diglycyl-l-tyrosyl and Hydrolysis by Chymotrypsin
Authors: Konishi Mitsuhiro , Yoshida Norio , Izumiya Nobuo
Published: July 2006

A cyclic hexapeptide, cyclo-(diglycyl-l-tyrosyl)2, was synthesized by several different routes; the cyclization reactions of a tripeptide active ester, a tripeptide azide, and a hexapeptide azide produced the desired cyclic hexapeptide. The cyclic peptide was hydrolyzed slowly by chymotrypsin to a tripeptide diglycyl-tyrosine, whereas a synthetic linear hexapeptide, diglycyl-l-tyrosyl-diglycyl-l-tyrosine, was hydrolyzed very rapidly to the tripeptide. Since the synthetic cyclo-(diglycyl-l-phenylalanyl)2 was insoluble in a buffer, it was not clear whether an incubation mixture of the substrate and enzyme yielded diglycyl-phenylalanine.
The Reactions of Complexes of Thioboronite with Compounds Containing Carbon-Nitrogen Multiple Bond
Authors: Mukaiyama Teruaki , Yamamoto Shoji , Inomata Katsuhiko
Published: July 2006

n-Butyl di-n-butylthioboronite reacts with isocyanates to give 1:2 adducts, and with isothiocyanate or carbodiimide to give a 1:1 adduct. It was found that thioboronite forms a 1:1 co-ordinated complex with benzyl cyanide, and that the complex reacts with isocyanates to give the corresponding acetamidine derivatives in good yields.
Preparation of p-Toluenesulfonyl Derivatives of myo-Inositol
Authors: Suami Tetsuo , Ogawa Seiichiro , Oki Shuichi
Published: July 2006

Six p-toluenesulfonyl esters of myo-inositol, five of which are new, have been prepared by a selective sulfonylation of myo-inositol derivatives and the structures of the new compounds were established by means of their proton magnetic resonance (PMR) spectra and the reaction sequences. Preparation of 1,3-di-O-p-toluenesulfonyl-myo-inositol, an useful intermediary compound for synthesizing myo-inosadiamine-1,3, has been improved by the present method.
Reaction Kinetics of the Redox Decomposition of Hydroxymercurated Propylene in Aqueous Solution Followed by Time-Sequential NMR Spectroscopy
Authors: Matsuo Masashi , Saito Yasukazu
Published: July 2006

The redox decomposition process of hydroxymercurated propylene in aqueous solution yielding acetone has been followed by time-sequential NMR spectroscopy in situ. No reaction intermediates and reaction products other than acetone were observed. Stoichiometric relationship holds between the reactant and the product during the reaction, which was verified by NMR spectra. The reaction rate was confirmed to be of first order with respect to mercurial. Although the rate was accelerated at higher acidity in solution, a similar rate enhancement took place by addition of neutral salts. At a certain ionic strength, no close linear correlation between the apparent rate constants and proton concentration was observed. In contrast, excellent linear dependence was obtained by the thermodynamic activities of the added electrolytes including acid. Since the apparent rate constant was independent of the concentration of free mercuric ion, a monomolecular mechanism is proposed. Taking into account the rate dependence upon added electrolytes, the redox decomposition of the hydroxymercurated olefins to give carbonyl compounds seems to proceed only when an aquo ligand is removed from the carbon-bonded mercuric ion.
Studies on Microcapsules. XI. Electrophoretic Behavior of Polyphthalamide Microcapsules Containing Aqueous Solution of Bovine Serum Albumin
Authors: Shiba Motoharu , Kawano Yasuaki , Tomioka Suiichi , Koishi Masumi , Kondo Tamotsu
Published: July 2006

Electrophoretic measurements were made on polyphthalamide microcapsules containing aqueous solution of bovine serum albumin and their membrane at various hydrogen ion concentrations. The microcapsules moved toward the anode at any pH, while the membrane migrated to the anode above pH 3.5 and to the cathode below this pH. These results were explained on the assumption that a fraction of albumin molecules is chemically incorporated into the microcapsule membrane through the microencapsulation and that the net electrical charge of the microcapsules is highly dependent on the charge of the outer surface of their membrane.
Photochemical Reactions of Uranyl Ions with Organic Compounds. IV. The Uranyl Fluorescence Quenching by Aliphatic Alcohols
Authors: Sakuraba Shukichi , Matsushima Ryoka
Published: July 2006

The relative rates for uranyl fluorescence quenching by aliphatic alcohols (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl alcohols) were measured under various conditions. The rates were increased in proportion to the perchloric acid concentration at pH <1, whereas the rates were smaller and nearly constant at the pH’s between 1–4; thus showing the involvement of both acid-dependent and acid-independent processes. Though the rates for both processes changed with the change in the alcohol structure (the polar substituent effect), the ratio of the two rate constants was nearly constant. The inhibitory effects of cupric ions (as a scavenger for the one-equivalent redox intermediates) suggested that the acid-dependent quenching process involves a two-equivalent redox or two consecutive one-equivalent redox steps between the same partners. The mechanisms of these quenching processes are discussed.
Desorption of Spread Monolayer of 1-Dodecanol into Aqueous Sodium Dodecyl Sulfate Substrate
Authors: Seimiya Tsutomu , Ohbu Kazuo , Nakamura Akio , Sasaki Tsunetaka
Published: July 2006

The process of desorption of dodecanol monolayer into the aqueous sodium dodecyl sulfate (SDS) solutions of varying concentrations was studied by the surface tension measurement. The rate of desorption in its early stage obeyed the simple diffusion law and the plot of logarithms of surface pressure against the square root of time showed a linear relationship. The rate constant of desorption decreased slightly and linearly with an increasing concentration of SDS up to CMC. Beyond CMC it increased rapidly and linearly owing to the increase of dodecanol solubility due to the solubilization. Further, from these rate constants and the surface tension vs. concentration curve, the diffusion coefficient of dodecanol in water and in aqueous SDS solutions, its solubilization in aqueous SDS solution and the partition coefficient of dodecanol between water and SDS micelles were calculated. Critical micelle concentration of sodium dodecyl sulfate was also determined as a break point of desorption constant vs. concentration curve.
Evidence of a Preresonance Raman Effect of the Base Residue in a Nucleic Acid
Authors: Tsuboi Masamichi , Takahashi Seizo , Muraishi Shuichi , Kajiura Teruo
Published: July 2006

The Ramam spectra of β-uridine-5′-phosphoric acid (UMP), its deuterated product, β-uridine-3′-β-uridine-5′-phosphoric acid (UpU), and polyribouridylic acid (poly U) have been observed in their aqueous solutions; and the Raman lines assignable to the phosphate group and to the base residue have been indicated. For UMP, the intensity ratio of a Raman line of the base residue versus that of the phosphate group was found to become greater on changing the exciting line from the 6328 Å line of a helium-neon laser to the 4880 Å line of an argon ion laser. This fact has been taken as indicating that a preresonance Raman effect takes place of the base residue with the effective absorption at 2600 Å.
Solvent Effects on the Spin-Lattice Relaxation Times and Chemical Shifts of N-Methylacetamide and N,N-Dimethylacetamide in Hydrogen Bonding Solvents
Authors: Sato Kazuo , Nishioka Atsuo
Published: July 2006

The proton spin-lattice relaxation and the chemical shift were studied in N-methylacetamide (NMA) and N,N-dimethylacetamide (DMA) in p-dioxane and chloroform. In the p-dioxane solution, it has been found that the self-association of NMA does affect its spin-lattice relaxation, whereas the amide-solvent association does not affect it entirely. This was interpreted in terms of the lifetime of the inter-amide (\simeq10−11–10−12 sec) and the amide-solvent association (much shorter than 10−11–10−12 sec). On the other hand, the effect of the amidesolvent association on the spin-lattice relaxation is pronounced in chloroform, as is the effect of the self-association of NMA. The inter-amide interaction which leads the double-bond character of DMA to be more stable was not reflected distinctly in the concentration dependence of the spin-lattice relaxation times of DMA.
An MO-theoretical Interpretation of the Nature of Chemical Reactions III. Bond Interchange
Authors: Fujimoto Hiroshi , Yamabe Shinichi , Fukui Kenichi
Published: July 2006

The wave functions of a system composed of two mutually-interacting molecules have been expressed in terms of configuration interaction wave functions. The electron configurations have been taken into account with respect to the states of adiabatic interaction, delocalization interaction, and polarization interaction. The electron populations in all of these states have been obtained separately. It has been demonstrated that the adiabatic interaction between two closed-shell molecules can not be the origin of the bond interchange in chemical reactions. The inclusion of charge-transferred states has been shown to be of great importance in explaining the formation of new bonds and the weakening of old bonds in the case of chemical interaction between two molecules. On the basis of the results of numerical calculations on some typical reaction models, the important role of the orbital overlapping interaction of the highest occupied molecular orbital and the lowest unoccupied molecular orbital has been pointed out.
Anodic Oxidation of Aniline in Aqueous Alkaline Solution
Authors: Matsuda Yoshiharu , Shono Akira , Iwakura Chiaki , Ohshiro Yoshiki , Agawa Toshio , Tamura Hideo
Published: July 2006

The anodic oxidation of aniline in an aqueous alkaline solution was studied. The anode materials were Ni, C, Pt, and Pb. An organic deposit (film) was formed on the anodes. The reaction mechanism was estimated through electrochemical measurements, chemical analysis, thin-layer chromatography, and UV, NMR, and IR spectrometries. The de-electronation of lone-pair electrons of the N atom in an aniline molecule caused the radical cation to be produced, (Remark: Graphics omitted.), and this process was the rate-determining step. Some of the radical cations were found to couple together to produce azo-benzene via hydrazobenzene. The other radical cations led to p-amino diphenylamine by head-to-tail coupling; this product was de-electronated again to give the polymer with a quinoid structure.
Mercury Photosensitized Reaction of Deuterio-Propylene Studied by Microwave Spectroscopy
Authors: Sakurai Yuzo , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The mercury photosensitized reaction of propylene-cis-1-d1 and 1-butene-cis-1-d1 was studied by means of microwave spectroscopy combined with gas chromatography and mass spectrometry. At pressures above 100 mmHg cis-trans isomerization was the main reaction for both the propylene and 1-butene. The number of the absorbed quanta of photons and the number of molecules reacted was almost equal. However, at lower pressures, this condition was not satisfied. At pressures less than 30 mmHg, substantial amounts of the 2-d1 and 3-d1 propylene species were detected in the reaction mixtures. Decomposition of propylene into an allylic radical and a hydrogen atom with subsequent “recombination,” was proposed to account for this observation. Similar results were obtained with 1-butene-cis-1-d1.
Re-examination of the Cycloaddition of Cycloheptatriene with Maleic Anhydride
Authors: Ishitobi Hiroyuki , Tanida Hiroshi , Tori Kazuo , Tsuji Teruji
Published: July 2006

Cycloaddition of cycloheptatriene to maleic anhydride was re-examined and found to produce, in addition to the reported main product anti-tricyclo[3.2.2.02,4]non-6-endo-8,endo-9-dicarboxylic anhydride (1), the exo, exo isomer of this compound (4) and bicyclo[3.2.2]nona-2,6-diene-endo-8,endo-9-dicarboxylic anhydride (5). Evidence for these structures involving the orientation of the cyclopropane ring in 1 and 4 and the configuration of the carboxylic anhydride was provided by PMR spectroscopy using the intramolecular nuclear Overhauser effect and paramagnetic induced shift due to tris(dipivalomethanato)europium(III). The structure assignment by Alder and Jacobs for 1 was found to be correct, but not the one by Schenk et al The difference in free energies of activation leading to 1 and 4 was determined.
Far-infrared Reflection Spectra, Optical and Dielectric Constants, and Lattice Vibrations of Some Fluoride Crystals
Authors: Nakagawa Ichiro
Published: July 2006

The reflection spectra of the crystals of the NaCl structure (LiF, NaF, and NiO), the fluorite structure (CaF2, BaF2, and CdF2), and the rutile structure (MgF2 and MnF2) were measured. The optical and dielectric constants were derived from the measured reflectivities using the Kramers-Kronig transformation. The absorption indices (k) for these crystals are rather large and the peak values of the imaginary dielectric constants amount to 30.0 or more. However, unlike the ferroelectric substances such as oxide perovskites and rutile, these fluoride crystals do not show any anomalous dielectric behaviour. From the real and imaginary dielectric constants ε′(ν) and ε″(ν), the transverse and longitudinal frequencies for the lattice modes are determined. These frequencies are reasonably interpreted on the basis of the crystal structures and satisfy the Lyddane-Sachs-Teller relation. The effective charge on the positive and negative ions and the force constant associated with the short-range elastic force against the ion displacement are obtained for the cubic crystals.