bluuebunny/crossref_metadata_2025 huggingface dataset:
The Interaction of Oxygen with Organic Molecules. II. Oxygen Quenching of the Excited States of Adsorbed Aromatic Hydrocarbons
Authors: Ishida Hideyuki , Takahashi Hiroshi , Tsubomura Hiroshi
Published: July 2006

Quenching of phosphorescence and fluorescence of aromatic hydrocarbons adsorbed on powdered porous glass or silica gel have been examined as a function of oxygen pressure. It has been found that the phosphorescence quenching at low temperature can be explained mostly by assuming that only those aromatic molecules having an oxygen molecule or molecules within an effective interaction radius are nonphosphorescent (static quenching model). The fluorescence quenching occurs only at much higher oxygen pressures and it has been proposed that contact pairs between aromatic and oxygen molecules, which have shorter intermolecular distances compared to the distances effective for the phosphorescence quenching and give rise to the charge-transfer absorption bands, are relevant. It has been observed that the excimer fluorescence of naphthalene appearing at a higher sample concentration is more strongly affected by oxygen than the monomer fluorescence. The emission spectra from naphthalene-porous glass adsorbate immersed in liquid oxygen and nitrogen have also been examined. The formation of the singlet oxygen (1Δg or 1Σg+) through the interaction of oxygen with triplet molecules has been confirmed by use of the peroxidation reaction of adsorbed anthracene.
On the Preparations of Metal Complexes. V. The Preparations of Cholatoamminecomplexes of Cobalt(III) and Chromium(III)
Authors: Nakahara Masayoshi , Urushiyama Akio , Satoh Yasuo , Kondo Yukio
Published: July 2006

The mono-, di- and tricholatocobalt(III) and chromium(III) complexes and cobalt complex cholates, including the following new compounds, have been prepared: [Co chol (NH3)5] X2 (X=chol, Cl), [M chol2 en2]Cl (M=Co, Cr), [Co chol3 (NH3)3] and [Co en3]chol3. The absorption spectra of these complexes in the visible, ultraviolet, and infrared regions have been measured and compared with those of the corresponding acetato- or acido-complexes.
Photoinduced Reactions. XLII. Homolytic Expulsion of 4-Substituent in the Photochemical Reaction of 2,5-Cyclohexadienones
Authors: Ogura Katsuyuki , Matsuura Teruo
Published: July 2006

Irradiation of 2,4,6-tri-t-butyl-4-bromo-2,5-cyclohexadienone (X) in various solvents yielded 2,4,6-tri-t-butylphenol (XIII) in high yields. It was shown that 2,4,6-tri-t-butylphenoxy radical (XII) was formed as an intermediate and that the light of shorter wavelengths than 450 mμ accelerated the hydrogen abstraction of XII. The rate of the photochemical decomposition of X decreased in the order: n-hexane, N,N-dimethylformamide and acetic acid. This and the sensitized reaction suggest that the formation of XII from X may result from the n-π* triplet state of X. On the other hand, irradiation of 2,4,6-tri-t-butyl-4-nitro-2,5-cyclohexadienone (XI) afforded 2,6-di-t-butyl-p-quinone (XV) and 2,4,6-tri-t-butylphenol (XIII), indicating a homolytic cleavage of the C–NO2 bond.
Studies of the Reissert-Kaufmann-type Reaction of 4-Nitropyridine N-Oxide and Its Homologues
Authors: Matsumura Eizo , Ariga Masahiro , Ohfuji Takahiko
Published: July 2006

The Reissert-Kaufmann-type reaction of substituted N-methoxy-4-nitropyridinium methylsulfates gave the corresponding 2-cyano-4-nitropyridines in satisfactory yields. When 3-methyl-4-nitropyridine N-oxide was used as the starting material, a cyano group was introduced not into the 6-position, but into the 2-position. This preference may be explained by proposing a hyperconjugation effect of the 3-methyl group. The resulting nitriles were quantitatively hydrolyzed to the corresponding 4-nitropicolinic acids. These reactions provided a new route for the preparation of nitropyridinecarboxylic acids from pyridine homologues. Further, some nucleophilic substitution reactions of the products were carried out.
Radiative Lifetime Measurements of N2(C3IIu), NH(A3II) and NH(C1II)
Authors: Sawada Tsuguo , Kamada Hitoshi
Published: July 2006

The radiative lifetimes of N2(C3IIu), NH(A3II), and NH(C1II) states were measured by the use of the time-sampling technique. The excited molecules were produced by the electron bombardment of N2 and NH3 gas. The lifetimes obtained in this experiment for N2(C3πII), NH(A3II), and NH(C1II) were (4.8±0.3)×10−8 sec, (4.1±0.2)×10−7 sec, and (4.3±0.2)×10−7 sec respectively. The oscillator strengths of the respective transitions were also calculated.
Measurement of Negative Ions Formed by Electron Impact. VII. Negative Ion Mass Spectra from Alkyl Cyanides
Authors: Tsuda Satoru , Yokohata Akira , Umaba Toshikatsu
Published: July 2006

The negative ion mass spectra from alkyl (methyl, ethyl, n- and iso-propyl) cyanides with electron energies of 80 eV, 40 eV and 9.5 eV were measured by a Hitachi RMU-6D mass spectrometer with emphasis on the relative abundance of negative ions to positive ions with electron energies of 80 eV, 40 eV and 15 eV. In every sample, the electron impacts with 80 eV and 40 eV gave almost the same distribution of m⁄e for negative ion mass spectra. Then, the peak of m⁄e 26(CN ) ions was the most intense and also the relatively strong peak of 25(C2H−) ions was found through all samples. On the other hand, the formations of 38(C2N−), 39(CHCN−) and 41(CH3CN−) ions from methyl cyanide, of 50 (C3N−) ions from ethyl cyanide, n- and iso-propyl cyanides, of 40(CH2CN−) ion from n-propyl cyanide were characteristic of each sample. The ratio of the yield of negative ions to positive ions was respectively of the order of ∼104 for CH3CN+/CN− (CH3CN), C2H4+/CN− (C2H5CN), C3H5+/CN− (n-C3H7CN) and C3H6+/CN− (iso-C3H7CN) at 80 eV and 40 eV electron energies. At 9.5 eV, m⁄e 26 (CN−) ions predominated over other negative ions for all the samples and a much larger peak of 40 (CH2CN−) ions in n-C3H7CN than in iso-C3H7CN was also observed. Then, we got the values of 19∼65 for CH3CN+/CN−, C2H4+/CN−, C3H5+/CN− and C3H6+/CN− (15 eV for positive ions). This work also gave linear relationship of the yield of each negative ion to the pressure in the range used for an usual chemical analysis.
The Stability of Fused Rings in Metal Chelates. VII. Copper(II) Complexes of Schiff Bases Derived from 2-Acetylpyridine or Pyridine-2-aldehyde and Dipeptides Containing Glycine, β-Alanine and/or α-Aminoisobutyric Acid
Authors: Nakao Yasuo , Ishibashi Hiroyuki , Nakahara Akitsugu
Published: July 2006

Eight new copper(II) complexes of SchifF bases derived from 2-acetylpyridine or pyridine-2-aldehyde and dipeptides containing glycine, β-alanine and/or α-aminoisobutyric acid have been prepared, and their relative stability was discussed on the basis of numerical data obtained by spectrophotometric, polarographic and other measurements. As a result, it was found that the stability of fused-ring systems decreases in the order 5-5-6-\simeq5-6-5->5-5-5->5-6-6-system (the first number represents the number of ring members containing pyridine derivatives and the second and third numbers represent those of ring members containing dipeptide moieties). The conclusion proposed previously that SchifF base chelates of aldehydes are generally less stable than those of corresponding ketones, has been proved to be valid also for the copper(II) chelates. It was found that transamination reactions take place in the copper(II) chelates of Schiff bases with pyridine-2-aldehyde and glycylglycine or glycyl-β-alanine.
Aromatic Metalation Reactions by Palladium(II) and Platinum(II) on Aromatic Aldoximes and Ketoximes
Authors: Onoue Hiroshi , Minami Kyoji , Nakagawa Kunio
Published: July 2006

Ortho metalation by palladium(II) was observed in the reaction of lithium tetrachloropalladate(II) with various aromatic aldoximes and ketoximes in methanol in the presence of sodium acetate. The obtained chloro-bridged complexes(7) possessed both ortho-attached palladiumcarbon σ-bonding and palladium-nitrogen coordinate bonding to oximes. Reactions of O-acyl and O-methyl oximes with lithium tetrachloropalladate(II) were also carried out. An ortho metalation was observed in the former case, but dichlorobis(O-methyl oxime)palladium(II) type complexes containing no palladium-carbon σ-bonds were predominantly formed in the latter case. The bridge-splitting reaction of chloro-bridged complexes with triphenylphosphine and the metathetic reaction with sodium bromide in acetone were carried out. In the case of potassium tetrachloroplatinate(II), an ortho metalation reaction was observed giving the complexes(10) but chloro-bridged complexes could not be isolated.
A Study of the Partial Catalytic Oxidation of Hydrocarbons. V. The Effect of Phosphorus Addition to the Vanadium Catalyst on the Oxidation of Butene, Butadiene, and Furan
Authors: Ai Mamoru
Published: July 2006

In the present investigation, the vapor-phase partial oxidation of cis-2-butene, butadiene, and furan was carried out over V2O5 and V2O5-P2O5, (1 : 1.6 atomic ratio), with various contact times, at 350°C, and at the concentration of 0.6–1.6% in air, in order to elucidate the effect of phosphorus addition to V2O5, on the selectivity and mechanism of butene oxidation. Oxidation activity decreased remarkably with an increase in the phosphorus content. In the presence of phosphorus (P/V=1.6), selectivity for the C4H8→C4H6 step and C4H6→C4H4O step were considerably increased, from 46 to 88 and from 72 to 93 mol% respectively, while selectivity for the C4H4O→maleic anhydride (MA) step fell from 60 to 50 mol%, due to the increase in polymer formation. From the results, it was concluded that V2O5 and V2O5-P2O5 catalysts show similar oxidation activity with regard to butene, butadiene, and furan, and that the quantities of the intermediate products are fairly much affected by the activity of the catalyst as well as by the difference in reactivity between the starting material and the intermediate over the catalyst.
Synthesis of Poly-malonylpolymethylenes
Authors: Matsui Kiyotada , Murotani Sadaichi , Nojiri Tetsuro , Motoi Masatoshi
Published: July 2006

Treatment of acetic anhydride with aliphatic dibasic acid chloride in the presence of 3 equivalents of aluminum chloride in nitrobenzene at 50°C afforded a polymer with the structure assigned to poly-malonylpolymethylene, R–[(CH2)m–COCH2CO]n–(CH2)m–R, (R=–COOH and/or –COCH3, n=8–16). Polymalonyl-heptamethylene, -hexamethylene and -pentamethylene were prepared and their properties were recorded. The product obtained by the reaction of acetic anhydride with adipoyl chloride seems to have a few cross-linkings in its structure.
Structure and Reactivity of α,β-Unsaturated Ethers. XII. Cationic Copolymerization of Ring-Substituted Styryl Ethyl Ethers
Authors: Okuyama Tadashi , Asami Nobuhiro , Fueno Takayuki
Published: July 2006

Several ring-substituted derivatives of cis- and trans-styryl ethyl ethers were copolymerized with the unsubstituted trans ether in methylene chloride at −70°C with the use of boron trifluoride etherate as a catalyst. The ring substituents investigated include p-CH3O, p-CH3, m-CH3, p-Cl, and m-Cl. It was found that the effects of substituents on the polymerizability obey the Hammett ρσ relationship with reaction constants ρ=−2.4 and −2.0 for cis and trans isomers, respectively. The structure of the transition state of the cationic polymeization was discussed.
Crystal and Molecular Structure of Di-μ-chloro-bis(π-1-ethoxycarbonyl-2-hydroxyallyl)dipalladium(II)
Authors: Oda Kunio , Yasuoka Noritake , Ueki Tatzuo , Kasai Nobutami , Kakudo Masao
Published: July 2006

The crystal and molecular structures of di-μ-chloro-bis-(π- 1-ethoxycarbonyl-2-hydroxyallyl)-dipalladium, (C6H9O3PdCl)2 have been determined from the three-dimensional data. The crystals are triclinic; space group Pl; with one dimeric molecule per unit-cell; a=4.80, b=10.31, c=10.64 Å, α=117.4, β=102.3, and γ=84.1°. The final discrepancy index is 14.0% for 1208 reflections. The two palladium atoms are joined by two chlorine bridges to form a square planar arrangement. The molecule possesses a center of symmetry which coincides with a crystallographic center of symmetry in the crystal; the overall coordination scheme of the palladium atom is similar to that established for the π-allyl palladium chloride dimer. The dihedral angle between the plane of four atoms [Pd, Pd′, Cl, and Cl′] and the π-allyl plane is 108. There are intermolecular hydrogen-bonds between the enolic hydroxyl group of one molecule and the carbonyl-group of the other molecule related by the center of symmetry.
Mechanism of Hydrogenolysis. I. Effect of Methyl Substituent on the Demethylation Rate of Polymethylbenzenes
Authors: Amano Akira , Uchiyama Masao , Sato Yoshiki , Tominaga Hiroo , Arai Hiromichi , Kunugi Taiseki
Published: July 2006

Rates of demethylation of six different polymethylbenzenes have been measured, at 702°C and residence times ranging from 0.5 to 6.0 sec in the presence of five-fold in excess hydrogen, by using toluene as an internal reference. The rates per one equivalent methyl group were: 1.08 for p-xylene, 1.73 for o-xylene, 1.26 for 4-position of 1,2,4-trimethylbenzene, 1.87 for 2-position of 1,2,4-trimethylbenzene, 1.85 for 1-position of 1,2,4-trimethylbenzene, 1.20 for 1,3,5-trimethylbenzene, 2.22 for 1-positionof 1,2,3-trimethylbenzene, 3.25 for 2-position of 1,2,3-trimethylbenzene, 1.5 for 5-position of 1,2,3,5-tetramethylbenzene, 2.1 for 1-position of 1,2,3,5-tetramethylbenzene, and 2.8 for 2-position of 1,2,3,5-tetramethylabenzene. all the figures being expressed against the standard value of 1.00 for toluene. The observed accelerating effect of neighboring methyl groups on the demethylation rates of crowded reactant molecules has been correlated with modified superdelocalizability in z direction for radical aromatic substitution. The latter values calculated by the extended Hückel molecular orbital method were: 0.4070, 0.4116, 0.4908, 0.4169, 0.4124, 0.4116, 0.4131, 0.4133, 0.4148, 0.4204, 0.4120, and 0.4029 (toluene) in the order given above. The general parallelism between the observed and the theoretical values may be taken as a support not only of the extention of the concept of superdelocalizability to radical aromatic substitution, but also of our mechanistic interpretation on the key reaction of hydrogenolyses.
Microwave Spectrum of Ethylene Episulfone
Authors: Nakano Yuji , Saito Shuji , Morino Yonezo
Published: July 2006

Microwave spectra of normal, 13C-, and 34S-isotopic species of ethylene episulfone have been investigated. Analysis of the spectra shows that the molecule has the C2V symmetry. The structural parameters obtained from the spectral data for the normal and 13C-ethylene episulfone are: r(C–C)=1.590±0.011 Å, r(C–S)=1.731±0.006 Å, r(S–O)=1.439±0.006 Å, ∠CSC=54°40′±15′, and ∠OSO=121°26′±30′, on the assumption that the C–H distances and the ∠HCH and ∠H2CC angles are the same as those of ethylene sulfide. Stark-effect measurements have yielded a value of 4.41±0.05 D for the dipole moment along the a axis. The structure obtained has been compared with those of other related molecules.
Frequency Distribution, Specific Heat, and Young’s Moduli of Orthorhombic Polyethylene with Skeletal Approximation
Authors: Kitagawa Teizo , Miyazawa Tatsuo
Published: July 2006

In preliminary studies on the frequency distribution, specific heat and Young’s moduli of the orthorhombic polyethylene crystal, methylene groups were treated as single dynamic units. Intermethylene force constants were estimated from the intermolecular potential function of methane and from deBoer’s potential function. Dynamical matrices of acoustic vibrations were constructed. A practical method was worked out for deriving the frequency distribution of acoustic vibrations from the volume enclosed in constant-frequency surfaces in a three-dimensional phase-difference space. With reference to specific heat in the lowest temperature region, inter-methylene force constants were adjusted. An efficient method was used for calculating the frequency distribution of crystal vibrations of chain-polymers. The frequency distribution of orthorhombic polyethylene crystal and specific heats in low temperature region were calculated in agreement with experimental results. A simple approximate method was used for treating Young’s moduli of orthorhombic chain-polymer crystals. Applicability of the skeletal approximation is discussed.
The Relation between the Amounts of Chemisorbed and Physisorbed Water on Zinc Oxide
Authors: Morimoto Tetsuo , Nagao Mahiko
Published: July 2006

In the system ZnO-H2O, in which a jump appears in the adsorption isotherm, the relation between the amounts of chemisorbed and physisorbed water has been investigated, on the basis of the measurements of the water adsorption isotherms and the water content. The first adsorption isotherm of water was measured at 18°C on a sample degassed at 450°C. After degassing the sample again at 30°C, the second adsorption isotherm was obtained at the same temperature as before. The water content (Vh) on the surface of the sample was determined by the successive ignition-loss method. In the present system, the amount of water physisorbed in the first layer is composed of two parts: one (Vp1) is the amount adsorbed at lower vapor pressures, up to the beginning of the jump in the isotherm, and the other (Vp2), the amount adsorbed during the jump. The amount of water chemisorbed (Vc) during the adsorption process could be estimated as the difference between the monolayer capacities of the first and second isotherms, the total amount of chemisorbed water being the sum of Vh and Vc. The ratio of the total amount of physisorbed water (Vp1+Vp2=Vp), expressed in the number of water molecules per unit of area, to that of chemisorbed water (Vc+Vh), expressed in the number of hydroxyl groups per unit of area, was found to be about 1 : 1 in the first physisorption layer for all the samples tested, irrespective of their origin, while the ratio of Vp1 to Vp2 varied extensively with the origin of the samples.
Electronic Structure of Lone Pairs. V. Thiothiophthene and 2,5-Dimethyl-dithiofurophthene
Authors: Yamabe Hiroko , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The electronic structure and the electronic transition of thiothiophthene(I) and 2,5-dimethyl-dithiofurophthene(II) are calculated by the semi-empirical ASMO SCF method. The EAB value, used instead of the bond order of the S···S bond of Compound I, and those of the S···S bond and the S···O interaction of Compound II are found to be −6.125 eV, −12.957 eV, and −0.740 eV respectively. These EAB values are compared with that of the previously-obtained transannular interaction and the hydrogen bond of water dimers calculated by the same method. The properties of the electronic transition of these compounds are discussed. No separability of the π–π*(B2)-type and σ-σ*(B2)-type transitions of the Compound I is indicated. The orbital energy of the highest occupied MO of the Compound I is remarkably high, which corresponds well with the very small Ip value.
Nuclear Magnetic Resonance in paramagnetic Solution. Proton Magnetic resonance Studies of Some Substituted Aniline Derivatives in the Presence of Paramagnetic Ni(II) and Co(II) Acetylacetonates
Authors: Yonezawa Teijiro , Morishima Isao , Akana Yoshinori , Fukuta Kazuhiko
Published: July 2006

To study the geometrical and electronic structures of molecules, the paramagnetic shifts of substiuted aniline proton resoances due to complexing with nickel of cobalt acetylacetonates, M(AA)2 (M=Ni or Co), were observed. The NMR spectra of sloutions containing an excess of niline derviatives and M(AA)2 show contact (for Ni(AA)2) and pseudocontact (for Co(AA)2)shift rations for various ligand protons. The contact shift ratios for N–H and N–CH3 protons reveal that the NH2 or NHR group of aniline dervatives is not coplanar with the aromatic ring for the coordinate molecules. This was confirmed by pseudo-contact shift studies.
An Application of the Oxidation Reaction between Ammonia and Bromate, Permanganate or Dichromate for the Determination of Ammonia Nitrogen in the Kjeldahl Digests without Distillation
Authors: Siddiqui M A , Bhatty M K , Ashraf Muhammad
Published: July 2006

Nitrogen in organic compounds, agricultural and animal products is converted into ammonium sulphate by Kjeldahl digestion. The ammonium sulphate is reacted quantitatively with hypobromite produced in situ by the addition of an excess of potassium bromate and bromide. The unutilized potassium bromate is determined iodometrically and the amount of ammonia nitrogen can be calculated from the consumed potassium bromate. Accurate results are also obtained when potassium bromate is replaced with potassium permanganate or dichromate for the determination of ammonia nitrogen in Kjeldahl digests. However, the present method is not applicable to the determination of ammonia nitrogen in undigested sample.
Kinetics of the Chromic Acid Oxidation of Glycollic and Benzilic Acids
Authors: Sengupta Kalyan K , Chatterjee A K , Moulik S P
Published: July 2006

The kinetics of chromic acid oxidation of glycollic and benzilic acids have been studied. Catalysis by H+ ions has been noticed in both cases of oxidation. The results show that the logarithm of the rate constants increases with increase in the proportion of acetic acid in the mixture. Ionic strength decreases the rate of oxidation. Pyridine catalyzes the oxidation of glycollic acid whereas the catalysis in the case of benzilic acid is negligible. The energy of activation and entropy of activation have been calculated. Both kinetics and spectrophotometric results indicate the formation of intermediate chromium (VI)-hydroxycarboxylate complex in each case. The complex finally decomposes to give reaction products. Glycollic acid initially produces glyoxylic acid which subsequently gives formic acid whereas benzilic acid is oxidized to benzophenone.
The Polarographic Behavior of Several α-Keto Acids in Buffered Solutions Containing o-Phenylenediamine, and Its Analytical Application
Authors: Wasa Tamotsu , Orita Morihiko , Yoshida Shingo , Musha Sôichirô
Published: July 2006

Such a-keto acids as glyoxylic (I), pyruvic (II), α-ketobutyric (III), mesoxalic (IV), oxalacetic (V), and α-ketoglutaric acid (VI) condense with o-phenylenediamine (OPD) to form two kinds of products, depending on the pH values of the reaction mixtures. The condensation product formed at pH values lower than 4 gives a well-defined reduction wave (E1⁄2  vs. SCE at pH 2.0: −0.490 V for I, −0.587 V for II, −0.592 V for III, −0.181 V for IV, −0.590 V for V, and −0.576 V for VI) at a potential more positive than that of free α-keto acid, while the other product, formed at pH values between 4 and 8, gives an oxidation wave (E1⁄2:−0.1–−0.2 V vs. SCE for all α-keto acids at pH 6.0). From the present polarographic investigations, it was deduced that the condensation product giving the reduction wave is probably 2-hydroxyquinoxaline derivatives and that the product giving the oxidation wave is benzimidazoline derivatives. A linear relation was obtained between the wave height for the reduction of the condensation product and the concentration ((0.5–20)×10−4  m) for each α-keto acid under appropriate conditions. The reduction wave of the condensation product was used for the determination of II in a commercial product containing II as an impurity.
The Reaction of β-Nitroalcohols and Reactive Aldehydes
Authors: Yoshimura Juji , Iida Takao , Funabashi Masuo
Published: July 2006

Condensation of acyclic or cyclic β-nitroalcohols with aldehydes was examined. In the case of non-protected 1-deoxy-1-C-nitro-d-glycitols and benzaldehyde, products caused by aldehyde-exchange reaction were obtained. However, the reaction of 2-methoxy-1-nitropentane or non-protected 2-nitrocyclohexanol and reactive aldehydes (formaldehyde, acetaldehyde and n-butyl glyoxylate) in the presence of sodium hydrogencarbonate gave the corresponding condensation products.
Oxidation by Transition Metal Complexes. II. Oxidation of Styrenes Catalyzed by Rhodium Compounds
Authors: Takao Kiyotomi , Wayaku Masami , Fujiwara Yuzo , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

Catalytic activities of chlorotris(triphenylphosphine)rhodium(I) and rhodium(III) chloride for the oxidation of olefins have been studied. It has been found that the complex and RhCl3 can cause catalytically the oxidation of aliphatic olefins such as styrene, α-methylstyrene or β-methylstyrene to produce carbonyl compounds under oxygen atmosphere. A remarkable solvent effect was observed in the reaction.
Study on Oxazolopyrimidines. V. Preparation of 9-Substituted Hypoxanthines via 7-Aminooxazolo[5,4-d]pyrimidines
Authors: Ohtsuka Yozo
Published: July 2006

Reaction of 4-cyano-5-ethoxymethylenaminooxazoles with aliphatic amines gave 7-alkylaminooxazolo[5,4-d]pyrimidines. The structure of these compounds was discussed on the basis of spectroscopic properties. These oxazolopyrimidines were converted to 9-alkylhypoxanthines by treatment with aqueous alkali (Method A) or by heating in formamide (Method B). Reaction of the ethoxymethylenamino compounds with aromatic amines gave 9-arylhypoxanthines directly (Method C).
The Properties of Aqueous Solutions of Sodium 2-Sulfoethyl Alkanoates and Sodium Alkyl β-Sulfopropionates
Authors: Hikota Takeshi , Morohara Kiyoshi , Meguro Kenjiro
Published: July 2006

A series of sodium 2-sulfoethyl alkanoates RCOO(CH2)2SO3Na was prepared from sodium isethionate and fatty acids containing 9, 11, 13, and 15 carbon atoms. The Krafft point, the critical micelle concentration (CMC), the surface tension, the emulsifying power, the wetting time, the resistance to acid hydrolysis, and the calcium-ion stability of this series of surfactants were examined, and the results were compared with those of the corresponding sodium alkyl β-sulfopropionates ROCO(CH2)2SO3Na, which have another structure of ester-linkage. The CMC values of sodium 2-sulfoethyl alkanoates almost coincide with those value of the sodium alkyl β-sulfopropionates with the same number of carbon atoms. However, the Krafft point and surface tension at the CMC of sodium 2-sulfoethyl alkanoates were lower than those of the sodium alkyl β-sulfopropionates with the same number of carbon atoms. Sodium 2-sulfoethyl alkanoates are more stable than sodium alkyl β-sulfopropionates in their resistance to hydrolysis and to the calcium-ion.
Isotope Effect of Molten Thallous Nitrate in Countercurrent Electromigration
Authors: Okada Isao , Saito Nobufusa
Published: July 2006

The isotope effect of the thallous ion in the countercurrent electromigration of molten thallous nitrate has been measured at 219°C. The relative internal mobility difference between 203Tl+ and 205Tl+, ΔV⁄VTl, has been determined to be 0.00035±0.00002. The mass effect μTl=(ΔV⁄VTl)⁄(ΔM⁄MTl), has been calculated to be −0.035±0.002, and this value has been compared with those of alkali nitrates previously determined.
Chromium(III) Complexes with Iminodiacetic Acid or l-Aspartic Acid
Authors: Mizuochi Hisayuki , Shirakata Shuichi , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The formation constants of chromium (III) complexes with iminodiacetic acid (IDA) and l-aspartic acid (Asp) as the terdentate ligands were determined by the pH method in the ionic strength, μ=0.1 and at 25°C: their values were logk1=10.9 and logk2=10.5 for IDA and logk1=10.1 and logk2=9.5 for Asp, respectively. That the overall formation constants of chromium(III)-IDA complexes obtained were slightly larger than those of the corresponding -Asp complexes was explained by the stronger chelate effect in the former complexes than in the latter ones. The solid chromium (III) complexes with IDA and Asp were also prepared. Based on chemical analyses and the conductivity measurement or the behavior toward the ion exchangers, the chemical formulas of these complexes are possibly K[Cr(ida)2]·3H2O and K[Cr(OH)2asp] respectively. X-Ray powder diffraction patterns indicated that the former crystalline complex has tetragonal unit lattice, the axial parameter being a=14.57 and c=12.38 Å, whereas the latter is amorphous solid.
The Phosphorescence Processes in Pyrimidine and 2-Chloropymidine
Authors: Nishi Nobuyuki , Shimada Ryoichi , Kanda Yoshiya
Published: July 2006

The phosphorescence spectra of pyrimidine and 2-chloropyrimidine have been observed at 4.2°K. A detailed vibrational analysis of the pyrimidine spectrum suggests that the emission arises from two components of the emitting triplet state. The phosphorescence lifetimes of pyrimidine and 2-chloropyrimidine have been measured for the 0-0 band and the strongest “vibronic band” (the phosphorescence maximum), which involves various modes of vibrations, at different temperatures between 77 and 1.5°K. The decay curve observed for the 0-0 band has been resolved into two exponential components, and that for the vibronic band, into three exponential components, where the third component was extremely weak in intensity at a very low temperature. From the comparison of the observed and calculated lifetimes of the individual phosphorescence components and their relative intensities, it was deduced that: (1) the 0-0 band involves emissions arising from the B2 and A1 components of the 3B1(n,π*) state, while the vibronic band involves an additional, third emission which very likely arises from the A2 component; (2) the 1A2(n,π*) state is located below the 1B1(n,π*) state; (3) the 3A1(π,π*) state is located below the 1A2(n,π*) state, and (4) the major intersystem crossing takes place from both the 1A2(n,π*) and 1B1(n,π*) states to the 3A1(π,π*) state in pyrimidine and 2-chloropyrimidine.
Stereochemistry of Trimethylenediaminetetraacetatocobaltate(III)
Authors: Ogino Hiroshi , Takahashi Masatake , Tanaka Nobuyuki
Published: July 2006

Conformation of trimethylenediaminetetraacetatocobaltate(III) (Cotrdta−) was inferred from the measurement of proton nuclear magnetic resonance spectra. It was found that K[Co-trdta]·2H2O crystals are mixtures consisting of equimolar amounts of the crystals of K[(+)546-Cotrdta]·2H2O and those of K[(−)546Cotrdta]·2H2O; that is, so-called “spontaneous resolution” was found. The absolute configuration of optically active Cotrdta was determined by the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) curves and by the reaction with ethylenediamine to form tris(ethylenediamine) cobalt(III) cation.
The Thermal Reaction of 3-Acetylguaiazulene with Sulfur
Authors: Kurokawa Shinji
Published: July 2006

When 3-acetylguaiazulene was heated with sulfur at 200°C, three new azulenoids were obtained, in addition to the S-guaiazulene formed by the loss of the acetyl group; the structures were established as 2-acetylguaiazulene, 6-acetyl-, and 7-acetyl-3,5,8-trimethylazuleno [6,5-b] thiophenes. From the experimental results it became obvious that a sulfur atom linked one methyl carbon atom of the isopropyl group with the C6-azulene-ring carbon atom in 3-acetylguaiazulene, resulting in the formation of a thiophene ring, and also that the loss and the migration of the acetyl group took place in 3-acetylguaiazulene as well. The acetyl migration in this compound was ascertained to be a simple thermal reaction and to occur in one direction, from C3 to C2.
Molecular Vibrations and Force Fields of Alkyl Sulfides. I. Dimethyl Sulfide and Its Deuterated Compounds
Authors: Shiro Yuji , Ohsaku Masaru , Hayashi Michiro , Murata Hiromu
Published: July 2006

Dimethyl sulfide and dimethyl sulfide-d1 were prepared, and their infrared spectra were measured in the gaseous and liquid states. The Raman spectra were measured in the liquid state. The assignments of their spectra were made. On these assigned frequencies, two sets of modified Urey-Bradley force constants and a set of local symmetry force constants were determined by a least-squares technique. The obtained force constants were then transferred to the treatment of the vibrational frequencies of dimethyl sulfide-d3. The centrifugal distortion constants obtained from the vibrational data were compared with those from the data of the microwave spectra in order to confirm the reasonableness of the obtained force constants.
Molecular Vibrations and Force Fields of Dimethyl Selenide and Dimethyl Selenide-d6
Authors: Shiro Yuji , Ohsaku Masaru , Hayashi Michiro , Murata Hiromu
Published: July 2006

A set of the modified Urey-Bradley force constants and of the local symmetry force constants of dimethyl selenide have been calculated by a least-squares technique, using the vibrational frequencies of the two isotopic species, (CH3)2Se and (CD3)2Se. The calculated frequencies thus obtained are in good agreement with the observed values. Comparison has been made for the force constants among dimethyl ether, dimethyl sulfide, and dimethyl selenide. This has shown the reasonable relation to be expected among the force constant, the bond length, the bond angle, and the atomic number of the central atom. The centrifugal distortion constants, which were calculated from the two sets of force constants, were then compared with those obtained from the microwave spectra; their values are found to be consistent with those obtained from a microwave study in a three-body approximation.
Optical and ESR Studies on Triphenylimidazolyl Radicals Produced by Photolysis and Radiolysis at Low Temperature
Authors: Shida Tadamasa , Maeda Koko , Hayashi Taro
Published: July 2006

The characteristic temperature-dependent behavior exhibited by the solution of the photochromic dimer of triphenylimidazolyl (photo-dimer) has been reinvestigated by means of optical and ESR spectroscopy. Assuming two conformations for triphenylimidazolyl radical, the spectral change at low temperatures has been elucidated in terms of a conformational isomerization of the radical and dimerization of the radical to a colorless dimer. Photo-dimer in γ-irradiated glassy solutions undergoes a dissociative electron attachment to produce triphenylimidazolyl radical and its anion.
The Crystal Structure and the Molecular Behaviour of 2,3-Dibromo-2,3-dimethylbutane at Room Temperature
Authors: Namba Yoshiyuki , Oda Tsutomu , Fukuda Nobuto , Takada Osamu
Published: July 2006

The crystal structure of 2,3-dibromo-2,3-dimethylbutane at room temperature has a disordered nature. In the crystal, trans-form molecules have at least four orientations of equal statistical weight around the axes parallel to the [001] direction. Therefore, in spite of the low symmetry of the molecule, the crystal belongs to the tetragonal system and has the space group of I4/mmm, while a=7.38 Å, c=8.12 Å and Z=2.
The Crystal Structure of cis-Dinitrotetraamminecobalt (III) Nitrate
Authors: Oonishi Isao , Fujimaki Hiroto , Muto Fumio , Komiyama Yoshimichi
Published: July 2006

The crystal structure of cis-dinitrotetraamminecobalt(III) nitrate, [Co(NO2)2(NH3)4]NO3, has been determined from three dimensional X-ray diffraction data. The dimensions of the orthorhombic unit cell are: a=12.19 Å, b=7.18 Å, c=10.92 Å, and Z=4. The space group is P212121. The structure has been refined by the three-dimensional Fourier and least-squares methods to R=0.095. The complex ion has a slightly distorted octahedral coordination, with six N atoms at 1.96±0.02 Å. The complexes are tightly bound together by N–H···O interactions, thus forming a three-dimensional network.
Substituent Effects on Spectral Properties of Protonated Azo Compounds
Authors: Eian G L , Kingsbury Charles A
Published: July 2006

The effect of a remote substituent upon the NMR and visible spectra, and upon hydrogen-deuterium exchange in certain phenylazophenol systems is reported. Electron donating substituents uniformly lower the NMR chemical shift function, Δδ, cause bathochromic shifts in the visible spectra, and increase the rate of deuterium exchange. Correlations between the above measurements and also with Hammett constants are reported. In particular the logarithm of t1⁄2 is linear with δO the chemical shift of the position adjacent to the position attacked by deuterium.
Hydrodynamic Voltammetry with the Convection Electrode. IV. The Measurements of the Kinetic Parameters of the Electrode Reaction. Part II
Authors: Suzuki Junsuke
Published: July 2006

The convection electrode system was applied to the determination of the kinetic parameters of the electrode reaction. By analyzing the observed current-voltage curve, the parameters of a and k° were calculated; for the ferric-ferrous system in 0.1m perchloric acid, α and k° were found to be 0.63 and 7.6×10−3 cm/sec respectively, while for the hexammine cobaltic-cobaltous system in 1m ammonia-ammonium chloride, they were 0.65 and 4.5×10−6 cm/sec respectively.
The Cation-exchange Separation of Nitrosylruthenium(III) from Ruthenium(III and IV) and Its Radiochemical Applications
Authors: Miki Eiichi , Ishimori Tatsujiro , Okuno Hisateru
Published: July 2006

The cation-exchange separation was made on a 0.1m perchloric acid solution of the evaporated residue of a hydrochloric acid solution which contained nitrosylruthenium(III) of 10 mg–100 μg Ru and ruthenium(III and IV) of 100–10 μg Ru; the nitrosylruthenium species were eluted by the use of 80–90 ml of 0.1m perchloric acid, and the ruthenium species, by the use of 100 ml of 3m hydrochloric acid containing 50 vol% ethyl alcohol for the columns (3–8 ml) of the HR type. It was found by means of the separation that a 106Ru-nitrosylruthenium tracer can be quantitatively prepared by passing nitric oxide into a hydrochloric acid solution of 106Ru-ruthenium(III and IV). The separation on dipotassium pentachloronitrosylruthenate(III) irradiated by thermal neutrons indicated that the specific activities caused by 103Ru in the ruthenium fractions are a few hundred times as high as those in the nitrosylruthenium fractions.
Synergistic Effect in Solvent Extraction—Effect of the Chelating Ligands on the Stability of Lutetium Mixed Chelates with β-Diketones and Their Adducts with TOPO—
Authors: Shigematsu Tsunenobu , Honjyo Takaharu
Published: July 2006

The effect of the chelating ligands on the stability of mixed chelates of lutetium with β-diketones and the stability of their adducts with TOPO in benzene was studied by extracting lutetium with mixtures of two β-diketones, benzoylacetone (BzA) and dibenzoylmethane (DBM), and benzoylacetone and benzoyltrifluoroacetone (BFA), in the absence or in the presence of TOPO. The results are summarized as follows. (1) The extraction constants of Lu-BzA-DBM mixed chelates are almost the same as statistically calculated, while those of Lu-BzA-BFA mixed chelates are somewhat lower than the theoretical values. (2) The stability of the TOPO adducts of the mixed chelates increases in the order, M(BzA)2(DBM)≈M(BzA)(DBM)2<M(BzA)2(BFA)<M(BzA)(BFA)2, which is almost the same as that found among the extraction constants of the mixed chelates. The fluoromethyl group stabilizes the adduct more than phenyl group. (3) All the mixed chelates of lutetium β-diketonates bind one molecule of TOPO per metal chelate.
The Thermal Annealing Behavior of Recoil Manganese Atoms Produced in Alkali Metal Permanganates by (n, 2n) and (n, γ) Reactions
Authors: Shiokawa Takanobu , Sasaki Teikichi
Published: July 2006

The thermal annealing behavior of recoil manganese atoms produced in alkali metal permanganates by 55Mn(n,2n)54Mn and 55Mn(n,γ)56Mn reactions was studied. In the case of potassium permanganate, the thermal annealing of 54Mn proceeded faster than that of 56Mn. The retention of 54Mn in the annealing curve decreased after an initial increase when it was treated at 180°C, whereas this anomaly was not observed in the case of 56Mn. These differences in the annealing behavior of the two nuclides were ascribed to the effects of background gamma radiation during the neutron irradiation and also to the differences in recoil energies. An effect of the counterpart cations of permanganate was also observed in the thermal annealing behavior, and was interpreted in terms of the ionization potential of alkali metal.
The Metal-Catalyzed Autoxidation of Cumene
Authors: Kamiya Yoshio
Published: July 2006

The catalysis of metal carboxylates and metal phthalocyanines in the autoxidation of cumene was kinetically studied. The limiting rate of oxidation of cumene was just over half the theoretical rate of kp2(RH)2/2kt suggesting that the induced decomposition of cumyl hydroperoxide due to cumyloxy radical proceeds rapidly. The effect of metal catalyst in the autoxidation of cumene was concluded to be caused by the decomposition of hydroperoxide and not by the activation of oxygen, since the rate of oxidation increased with the increase in the rate of metal-catalyzed decomposition of hydroperoxide. The synergistic effect on the metal-catalyzed autoxidation of cumene was proved to result from the synergistic effect of metal salts on the decomposition of hydroperoxide. The oxidation products of cumene varied remarkably according to reaction conditions.
Aromatic Substitution of Olefin. X. Formation of Biphenyl Derivatives by Means of Olefin-Palladium Chloride Complexes and Silver Nitrate
Authors: Fujiwara Yuzo , Moritani Ichiro , Ikegami Katsuhiko , Tanaka Ryohei , Teranishi Shiichiro
Published: July 2006

The system, olefin-palladium chloride complex-silver nitrate has been shown to cause the oxidative coupling reaction of the aromatic compounds to afford biphenyl derivatives. The mechanism was also discussed in connection with the aromatic substitution of olefins by palladium salts.
Syntheses of 2,3-Dihydro-4(1H)-pyridones
Authors: Sugiyama Noboru , Yamamoto Makoto , Kashima Choji
Published: July 2006

The condensation of β-diketones with benzaldazine yields 1-benzylidenimino-2,3-dihydro-4-pyridones, which may be catalytically hydrogenolyzed to the corresponding 2,3-dihydro-4(1H)-pyridones. Some reactions of 2,3-dihydro-4(1H)-pyridones are discussed.
Mechanism of Decomposition of Carboxylic Sulfurous Anhydrides
Authors: Kobayashi Michio , Minato Hiroshi , Ogi Yoshikuni
Published: July 2006

Ethyl benzoyloxysulfinate, prepared from 18O-labeled benzoic acid and ethyl chlorosulfite, was decomposed and the products were analyzed. The 18O analyses showed that; 1) prior to decomposition the 18O of the mixed anhydride was scrambled due to the formation and the internal return of an ion-pair, C6H5C+−OSOEt; 2) ethyl benzoate, benzoic anhydride and diethyl

(Remark: Graphics omitted.)

sulfite were produced via an ionic chain mechanism involving successive attack of ethoxide anion and benzoate anion on the carbonyl carbon and sulfinyl sulfur of the mixed anhydride.
Phosphorescence of Quinoxaline-Durene Mixed Crystal — Analysis of Fine Structures and Decay Characteristics
Authors: Nakano Yasuko , Azumi Tohru
Published: July 2006

The phosphorescence spectrum of quinoxaline doped in durene crystal is observed at 4.2°K. The spectrum is composed of a number of sharp bands, many of which being interpreted as arising from the coupling with the ground state molecular vibrations of quinoxaline. Associated with the 0,0 and vibronic bands three weak bands were observed which are separated from the vibronic band by 19, 30 and 52 cm−1. The nature of these three bands is not well understood, but it is certain that they are not due to the lattice vibrations of the durene host. The decay of the phosphorescence is investigated at fifteen different temperatures between 4.21 and 1.59°K. Above 2.41°K the decay is single exponential with a lifetime of 0.246 sec. Below 2.19°K, however, the decay is expressed as a sum of two exponential decays whose lifetimes are 0.757 and 0.093 sec. The shorter one is approximately one third of the lifetime at 4.21°K. The change of the decay characteristics at a temperature between 2.19 and 2.41°K is interpreted to be associated with the spin alignment. In terms of these data, together with the polarization ratio observed by Chaudhuri and El-Sayed, radiative and radiationless rate constants are estimated for each of the three magnetic subcomponents of the triplet state. The experimental results and their interpretation are partly in disagreement with the work by de Groot, Hesselmann and van der Waals, and the source of the discrepancy is analyzed.
The Dichroic Spectra of Hydroxy Derivatives of Naphthalene, Anthracene, and Phenanthrene in Polyvinylalcohol Sheets
Authors: Inoue Hiroyasu , Nakamura Takio , Igarashi Tetsutaro
Published: July 2006

The dichroic spectra of 1,4-dihydroxynaphthalene, 9-hydroxyanthracene, sodium 9,10-dihydroxyanthracene-2-sulfonate, and 9,10-dihydroxyphenanthrene, which were usually unstable in a liquid solution, were measured in stretched polyvinylalcohol sheets. From a comparison of the results of the dichroic spectra with those of the MO calculations, the polarizations of the electronic bands were determined, and the bands were assigned in terms of the relevant bands of the corresponding unsubstituted aromatic compounds.
The Liquid-phase γ-Radiolysis of Benzene-Nitrous Oxide Mixtures
Authors: Hirokami Shun-ichi , Shishido Seishi , Sato Shin
Published: July 2006

The γ-radiolysis of the benzene-nitrous oxide liquid mixtures has been studied at room temperature and at 0°C, the mixing ratios covering almost all the range from pure benzene to pure nitrous oxide. Phenol was found to be one of the main products; its G-value is about a half of that of nitrogen at the lower concentration of nitrous oxide. Kinetic analysis shows that the G-values of electrons from benzene are 3.2±0.2. An empirical equation for expressing the G-value of nitrogen from the benzene solution of nitrous oxide proposed by Hentz and Sherman (J. Phys. Chem., 73, 2676 (1969).) was examined. The agreement was very poor at higher concentrations of nitrous oxide. Possible reasons were discussed.
Studies on Triplet Energy Transfer by Means of an Emission-Absorption Flash Technique. II. Mixed Triplet-Triplet Annihilation in Ethanol
Authors: Kikuchi Koichi , Kokubun Hiroshi , Koizumi Masao
Published: July 2006

The mixed delayed fluorescence due to the processes, (Remark: Graphics omitted.) in the following systems in ethanol solutions have been quantitatively investigated, a) 1) 9-methylanthracene-anthracene, 2) 9-phenylanthracene-anthracene, 3) 9-methylanthracene-9-phenylanthracene, 4) anthracene-acridine, 5) 9-methylanthracene-acridine, 6) 9-phenylanthracene-acridine. b) 7) eosin-anthracene, 8) proflavine-anthracene, 9) eosin-acridine. It has been found that for class a) in which the separations of singlet excited levels of A and B are less than a few times of kT, the delayed fluorescence of both components occur and the value of (pMA+pMB is close to that of the efficiency of a simple p-type delayed fluorescence, pA or pB. The delayed mixed excimer fluorescence also occurs in most cases. For class b) in which the level differences largely exceed kT, only the delayed fluorescence of the lower level component occurs. It has also been established that the delayed excimer fluorescence in a single component system increases in intensity from anthracene through 9-methyl-to 9-phenylanthracene. The pMA/pMB values are discussed for systems (1), (2), and (3).
Synthesis and Spectral Properties of Chloro-substituted Triptycenes
Authors: Mori Ikuko , Kadosaka Tadao , Sakata Yoshiteru , Misumi Soichi
Published: July 2006

A series of 2-, 7-, 10-, and 11-chloro-substituted triptycenes were prepared by means of the addition of benzyne or 3-chlorobenzyne to anthracene and its derivatives for studying the effect of chloro-substituent on electronic and NMR spectra. It was found that the intensity of the longest wavelength bands in the chlorotriptycenes could be explained in terms of superposition of three benzenoid chromophores, and that the calculated value of chloro-group on magnetic anisotropy was in good agreement with the values reported.