bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Etherification Reactions of Allyl Alcohol Catalyzed by the Copper(I) Chloride Complex
Authors: Ogura Tetsuya , Furuno Nobuo , Kawaguchi Shinichi 
Published: July 2006

Abstract
Diallyl ether was produced exclusively when an allyl alcohol solution containing copper(I) chloride and ammonium chloride was heated in the absence of air. A mixture of allyl and ethyl alcohols gave diallyl and ethyl allyl ethers, but no trace of diethyl ether. The tracer experiment employing 18O-enriched allyl alcohol showed that the C–O bond in allyl alcohol was ruptured in the ethyl allyl ether formation. The kinetic study of these etherification reactions showed that the rate determining step would include the nucleophilic attack of an allyl or ethyl alcohol molecule on the catalyst-substrate complex. A novel allyl alcohol complex, (NH4)2Cu2Cl4(C3H6O)2, was isolated and characterized, but the active catalyst species was assumed to be (NH4)2Cu4Cl6. Methyl derivatives of allyl alcohol were also allowed to react in the presence of the same catalyst and the possible mechanism of etherification was discussed.
The Microwave Spectrum, Structure, and Dipole Moment of Ethylene Episulfoxide
Authors: Saito Shuji 
Published: July 2006

Abstract
The microwave spectra of the normal species as well as the 13C and 34S isotopic molecules of ethylene episulfoxide have been observed. The rotational constants thus obtained lead to the following structural parameters: S–O=1.483±0.003 Å, C–S=1.822±0.003 Å, ∠OSC=111°1′±10′, ∠CSC=48°46′±10′, on the assumption that the C–H distance and the ∠HCH and ∠H2CC angles are the same as those of ethylene sulfide. From the Stark shifts, the dipole moment has been determined to be μa=3.61±0.04 D, μc=0.89±0.01 D and μtotal=3.72±0.04 D. The bond nature of S–O and C–S has then been discussed on the basis of these data.
Chemical Effects Associated with β-Decay Process. IV. Kinetic Studies of the Chemical Behavior of 144Pr Decayed from the 144Ce(III)-Diethylenetriaminepentaacetate Complex
Authors: Shiokawa Takanobu , Omori Takashi 
Published: July 2006

Abstract
The chemical behavior of 144Pr as a result of the β−-decay of the 144Ce(III)-diethylenetriaminepentaacetate (144Ce(III)-DTPA) complex was investigated in detail on the basis of the substitution reaction mechanism. The experimental results, represented in terms of the yield of the 144Pr(III)-DTPA complex, were explained quantitatively by the application of Bateman’s equation. An increase in the nuclear charge in the β-decay of the 144Ce(III)-DTPA complex may result in the formation of 144Pr(IV)-DTPA, which would then be reduced to an intermediate complex of 144Pr(III) by an intramolecular electron-transfer. The mechanisms and the rate constants are established for the decomposition of the intermediate leading to the formation of the uncomplexed ion. It was also suggested that the uncomplexed 144Pr(III) ion is produced directly by an exhaustive bond-rupture of the daughter complex ion, without any formation of the intermediate. The ratio of bond-rupture was determined to be 0.25; this value is in accordance with the theoretical value for the formation of the multiply-charged 144Pr ion due to electron shake-off and the internal conversion of γ-rays, followed by the Auger process.
Electronic Spectra of Crystalline TCNQ Anion Radical Salts. I. Simple Salts
Authors: Iida Yôichi 
Published: July 2006

Abstract
The present paper deals with crystalline TCNQ, anion radical “simple” salts of M+ TCNQ\divdot, where M+ represents a diamagnetic counter cation. Their crystalline electronic spectra were measured in the range between 4.0 and 30.8 kK by means of diffuse reflectance. The crystalline spectra thus obtained were quite different from that of the TCNQ, radical anion monomer and exhibited a broad and intense low-energy band around 9 kK in the low-conductivity compounds and at 4.3 kK in the high-conductivity compound. These bands were ascribed to inter-radical charge-transfer in the solid state. The crystalline spectra were found to be closely correlated to their unusual electrical and magnetic properties. It was concluded that these physical properties were based on a unique TCNQ molecular arrangement in groups of several or an infinite number of face-to-face molecular systems.
Reactive Fiber. VII. Preparation and Polymerization of Vinyl Sulfonyl (β-Chloroethyl)amide
Authors: Iwakura Yoshio , Uno Keikichi , Nakabayashi Nobuo , Chiang Wen-Yen 
Published: July 2006

Abstract
Vinyl sulfonyl (β-chloroethyl)amide (III) was prepared from vinyl sulfonyl chloride and aziridine. The monomer reactivity ratios of III (M2) (r1=3.0, r2=0.075) were determined from the result of copolymerization with styrene (M1), and Q2 and e2 values calculated were 0.13 and 0.42 respectively. Radical polymerization of III gave a polymer with low viscosity and the polymer had good reactivity with nucleophilic reagents. To compare the functional group in polymer chain with that of monomeric compound, methane sulfonyl (β-chloroethyl)amide (IV) was prepared and the reaction between the function and several nucleophiles was studied. Reactive fibers were obtained from copolymers of acrylonitrile and III. Reaction of the fibers with Congo Red was carried out in the presence of pyridine.
Studies of Peptide Antibiotics. XIV. Analogs of Gramicidin S Containing d-Valine or d-Leucine in Place of d-Phenylalanine
Authors: Aoyagi Haruhiko , Kato Tetsuo , Waki Michinori , Abe Okitoshi , Okawa Reiko , Makisumi Satoru , Izumiya Nobuo 
Published: July 2006

Abstract
Two analogs of gramicidin S, 4,4′-d-valine- and 4,4′-d-leucine-gramicidin S (XVI-A and XVI-B), have been synthesized and tested for the antibacterial properties. The crude product obtained after the cyclization of a linear pentapeptide active ester was composed of the protected monomer and dimer. The pure protected dimer was obtained by a column chromatography of Sephadex LH-20, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of XVI-A or XVI-B. These analogs were as active as natural gramicidin S; the results indicated that the aromatic side chains of the d-phenylalanines in the molecule of gramicidin S can be replaced by the aliphatic side chains without an influence for the activity.
The Decomposition of Cyclohexyl Hydroperoxide in the Presence of Cyclohexanone and a Novel Rearrangement Product
Authors: Chubachi Sumio , Matsui Hideo , Yamamoto Kiyoshi , Ishimoto Sachio 
Published: July 2006

Abstract
One of the major reaction products besides cyclohexanol from the reaction of cyclohexyl hydro-peroxide with cyclohexanone was isolated and confirmed as ε-cyclohexyloxycaproic acid. The rate of formation of ε-cyclohexyloxycaproic acid was measured in excess cyclohexanone and found to follow a first order law for cyclohexyl hydroperoxide. The activation energy of 10.1 kcal/mol was found for the formation of the acid. The rate of decomposition of cyclohexyl hydroperoxide in cyclohexane was measured in the presence of various concentrations of cyclohexanone and the rates of formation of cyclohexanol and the free carboxylic acids were also measured. An adduct formation between cyclohexyl hydroperoxide and cyclohexanone followed by homolytic decomposition of the adduct was suggested to explain the experimental results.
Photochemical Ethoxycarbonylmethylation of Benzene with Ethyl Haloacetates
Authors: Ogata Yoshiro , Itoh Teruo , Izawa Yasuji 
Published: July 2006

Abstract
The ultraviolet light-induced reaction of ethyl haloacetate with an excess benzene gives ethyl phenylacetate (1.7%) and diethyl succinate (1.6%) as main products, while the same reaction of excess chloroacetate with benzene gives ethyl phenylacetate higher yield (optimum 78.4%). Addition of aluminum chloride to the reaction mixture using an excess benzene gives ethyl phenylacetate as a sole product (11.5%). The effect of reaction conditions on the yield is examined.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. V. Direct Synthesis of t-Amyloxycarbonyl- and t-Butyloxycarbonyl-amino Acids Using the Respective t-Alkyl Chloroformates
Authors: Sakakibara Shumpei , Honda Ichiro , Takada Katsumi , Miyoshi Muneji , Ohnishi Takanobu , Okumura Kentaro 
Published: July 2006

Abstract
t-Amyloxycarbonylamino acids (Aoc-amino acids) were found to be synthesizable under the conditions of the Schotten-Baumann reaction with t-amyl chloroformate in the presence of a water-soluble inert solvent. The procedure was applied to almost all amino acids or their derivatives; the yields of the products and their purities were satisfactory except in the cases of asparagine, glutamine, and nitroarginine. Many t-butyloxycarbonylamino acids (Boc-amino acids) were also synthesized successfully using the same procedure. Similarly, t-amyl and t-butyl carbazates were synthesized in satisfactory yields with these chloroformates and hydrazine hydrate. Thus, the procedure was demonstrated to be the simplest for the preparation of Aoc-or Boc-amino acids and hydrazide.
A Study on Electron Spin Resonance of the Complex between Metal Ions of Group II and o-Quinone Anion
Authors: Kuwata Keiji , Shimizu Yasuhiro 
Published: July 2006

Abstract
An electron spin resonance study on the complex formation between o-quinone anion and metal ions of group II was undertaken, and the change in g-factor and proton hyperfine splittings of o-quinone anion by the complex formation were examined in detail. The change in g-factor was closely related to both the change in the unpaired electron distribution and the change in energy difference between lone pair orbital of oxygen and unpaired electron orbital. The stabilization of the quinone anion against its coupling reaction was seemed to be related to the shift in g-factor by complex formation. The interaction between quinone anion and metal ions was deduced to be partly ionic. An open shell SCF calculation with CI for the free quinone anion was carried out in order to discuss the electronic spectra of the complex.
K-Band Electron Paramagnetic Resonance of Sulfur Monoxide in the Gaseous Phase
Authors: Uehara Hiromichi 
Published: July 2006

Abstract
Four K-band electron paramagnetic resonance transitions of 3Σ− 32S16O in the gas phase have been observed. One of these occurs between the Zeeman levels of the K=1, J=0→K=0, J=l states and three between the Zeeman levels of the K=2, J=2→K=3, J=2 states. The analysis of the spectra has led to the g values of gse, gle, and gr (in accordance with the notation by Tinkham and Strandberg). Knowledge of the rotational magnetic moment gave the equilibrium internuclear distance of Re=1.48101±0.00006 Å.
Fragmentation of the Excited Isobutane Ion Produced by Charge Transfer from the Nitrogen Molecule Ion
Authors: Miyazaki Tetsuo , Kohama Tadahiko , Fueki Kenji , Kuri Zen-ichiro 
Published: July 2006

Abstract
The radiolysis of the N2-isoC4H10 (0.0153 mol/mol of N2) mixture has been studied by using such ion scavengers as ammonia and sulfur hexafluoride. It was found that the C3H7+ ion is formed by the fragmentation of the excited isobutane ion produced by the charge transfer from the nitrogen ion. Although nitrogen is an effective quencher of the excited ion, the yield of the C3H7+ ion is constant over the pressure range from 0.66 to 130 atm. It has been concluded that the excited isobutane ion produced by the charge transfer with 5 eV excess energy decomposes very fast and that it can not be deactivated by nitrogen of 130 atm, while it has been reported by other authors that the excited isobutane ion with 1.2 eV excess energy can be deactivated below 1 atm. This difference in the characters of the excited isobutane ions can be explained by the previously-proposed mechanism of the fragmentation.
Photochemistry of Acetanilide. IV. The Photochemical Reactions in the Vapor Phase and Rigid Matrixes
Authors: Shizuka Haruo , Tanaka Ikuzo 
Published: July 2006

Abstract
The photolysis of acetanilide in the vapor phase at 2537 Å and 120°C has been studied by means of mass spectrometry, gas chromatography, and spectrophotometry. In the vapor phase, no such rearrangements of acetanilide as in the liquid phase occurred, only the decomposition of acetanilide. Carbon monoxide and ethane were formed as the main products, and the ratio of carbon monoxide to ethane was about 2. The quantum yield of the predissociation for the N–C bond of acetanilide in the vapor phase was estimated to be 0.28 from the data of the quantum yields for the formations of carbon monoxide and ethane. A small amount of methane and traces of hydrogen and benzene were also detected. The reaction scheme of acetanilide in the vapor phase at 2537 Å and 120°C has been proposed. On the other hand, the photochemical reactions of acetanilide in the rigid matrixes (MP, ME, and EPA) at −196°C and in the PVA sheet at room temperature have also been carried out by the use of a spectrophotometer and an ESR spectrometer. In the rigid matrixes at −196°C, the photochemical rearrangements did not occur, only the back reaction resulting in the distortional structure of acetanilide; this mechanism can be explained by the stiffness of the solvent cage. The cage effect on the photochemical reaction of acetanilide is also discussed.
Solubility of Chlorine in Mixed Solutions of HCl and CuCl2
Authors: Hine Fumio , Inuta Shusei 
Published: July 2006

Abstract
The solubility of chlorine in a mixed solution of HCl and CuCl2 under various conditions of concentration, temperature, and partial pressure was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3− was found to be proportional to the partial pressure of chlorine in the gas phase; its slope decreased with an increase in the concentration of cupric ions due to the salting-out effect.
Fluorescence Lifetime of Acridine in Water-Organic Solvent Mixtures
Authors: Kokubun Hiroshi 
Published: July 2006

Abstract
Fluorescence lifetime of acridine has been measured in water-ethanol and water-glycerol mixtures of different composition at 25°C. Remarkable decrease in lifetime value was found as the amount of organic component increases. The lifetime of 10.3 ns was obtained for the aqueous solution. The lifetimes in glycerol and in ethanol were determined as 3.2 and 0.72 ns, respectively. The observed ratio of the lifetime in the mixture to the lifetime in water, τ⁄τ0, has the same functional dependence on solvent composition as the ratio of fluorescence yield, Φ⁄Φ0. These quenching phenomena by organic molecules have been interpreted as due to the solvent effects upon the radiationless transition rate. Both static and dynamic mechanisms of quenching are not applicable in the present cases of solvent quenching.
Determination of a Small Amount of Iodide by Atomic Absorption Spectrophotometry Using a Cadmium Hollow Cathode Lamp
Authors: Kumamaru Takahiro 
Published: July 2006

Abstract
A new application of atomic absorption spectrophotometry to the determination of iodide has been proposed. The method is based on solvent extraction into nitrobenzene of the colorless ion-pair formed between tris(l,10-phenanthroline)cadmium(II) and the iodide anion, and the subsequent determination of the cadmium concentration in the extract by atomic absorption in an air-acetylene flame at the 2288 Å cadmium line. The absorbance due to cadmium in the extract shows a linear relationship to the concentration of iodide over the range from 4×10−6 to 4×10−5 m initially present in the aqueous solution. The optimum conditions for the determination of iodide have been established, and the extraction efficiency and the effect of other anions have also been studied.
Acid Decomposition of Metal Xanthate Complexes and Their Stability Constants
Authors: Nanjo Michio , Yamasaki Taro 
Published: July 2006

Abstract
The formation of 1 : 1 complexes was confirmed by means of the kinetic method. The acid decomposition of xanthate was delayed by the addition of metal ions because of the decrease in the concentration of ethyl xanthic acid in an equilibrium. By using the rate equation, the stability constants were found to be (1.0±0.2)×104, (1.7±0.4)×10 and (2.5±0.4)×104 for Cd(EX)+, Zn(EX)+, and Pb(EX)+ respectively.
Excitation Transfer in the Radiolysis of Solid Hydrocarbons as Studied by ESR Spectroscopy and Product Analysis
Authors: Wakayama Terunobu , Kimura Toyoaki , Miyazaki Tetsuo , Fueki Kenji , Kuri Zen-ichiro 
Published: July 2006

Abstract
The effect of carbon tetrachloride on the radiolysis of isobutane and methylcyclohexane at 77°K is studied by ESR spectroscopy and by product analysis. The yields of solvent radicals from the γ-irradiation of isobutane and methylcyclohexane are not changed by the presence of conventional electron scavengers. This indicates that solvent radicals are not formed by the neutralization of solvent cations with electrons. On the contrary, the yields of solvent radicals decrease remarkably upon the addition of CCl4. Though the yield of propylene from the γ-irradiation of isobutane is not affected by the addition of electron scavengers, it decreases significantly upon the addition of CCl4. Though the decrease in the hydrogen yield in the radiolysis of methylcyclohexane at 77°K upon the addition of electron scavengers is only about 1G-unit, it amounts to more than 3.5G-units upon the addition of CCl4. These characteristic effects of CCl4 can possibly be explained in terms of excitation transfer from the excited solvent molecule to CCl4. A kinetic treatment suggests that its mechanism may be an exciton transfer.
The Zero-point Average Structure of Acetone
Authors: Iijima Takao 
Published: July 2006

Abstract
The zero-point average structure of acetone has been determined from the moments of inertia obtained by means of microwave spectroscopy by Nelson and Pierce, as incorporated with the average distances from gas-electron diffraction by Kato et al. In addition to the normal species (CH3)2CO, three isotopically-substituted species, (13CH3)2CO, (CH3)2C18O, and (CD3)2CO, have been used in the analysis. The following values of the rz-parameters have been determined: C=O, 1.2122±0.0025 Å; C–C, 1.5190±0.0008 Å; C–H, 1.0614±0.0010 Å; ∠HCH, 108°30′±6′; and ∠CCC, 116°9′±10′ (∠CCC for (CD3)2CO, 115°51′±10′). The slightly smaller value of ∠CCC found for the deuterated species has been reasonably attributed to the anharmonicity associated with the symmetric rocking motion of the two methyl tops. The equilibrium values for C-H(D) and ∠CCC have also been estimated to be 1.078 Å and 115°0′ respectively.
Solvent Effect on the Electronic Spectra of Bis(8-quinolinolato)- nickel(II) at 80°C
Authors: Moriguchi Yoshiki , Ueno Keihei 
Published: July 2006

Abstract
The visible absorption spectra were observed on bis(8-quinolinolato)nickel(II) in molten 8-quinolinol as well as in other solvent systems such as molten naphthalene, molten β-methoxynaphthalene or toluene containing various amounts of 8-quinolinol at 80°C. Little interaction was found between the solute and naphthalene or toluene. However, a weak interaction was observed between the solute and β-methoxynaphthalene or 8-quinolinol. The extent of interaction between the solute and 8-quinolinol in toluene was evaluated spectrophotometrically.
Cobalt(II) Complexes with Nitrilotriacetic Acid, Nitrilopropionicdiacetic Acid and Nitriloisopropionicdiacetic Acid
Authors: Tachibana Mitsuo , Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The following cobalt (III) complexes containing nitrilotriacetic acid (NTA), nitrolopropionicdiacetic acid (NPDA) and nitriloisopropionicdiacetic acid (NIPDA) were prepared: (NH4)3[Co-(nta)2]·2H2O (pink) (I), NH4[Co(Hnta)2]·2H2O (pale pink) (II), K3[Co(npda)2]·2H2O (pink) (III), K[Co(Hnpda)2]·3H2O (pale pink) (IV), [Co(npda)(o-phen)]·H2O (reddish violet) (V), [Co-(npda)(bipy)] (reddish violet) (VI), K[Co(OH)(nipda) (H2O)]·H2O (bluish violet) (VII) and [Co-(nipda) (o-phen)] (reddish violet) (VIII); where nta, npda, nipda, o-phen and bipy are the abbreviations of nitrilotriacetate-, nitrilopropionicdiacetate-, nitriloisopropionicdiacetate-ion, o-phenanthroline and 2,2′-bipyridyl, respectively. On the basis of electronic spectra, it was found that complexes I to IV have the trans form, while complexes V, VI and VIII have the mer form structure with respect to the nitrogen atoms in the coordinating ligands. Complex VII showed a dehydrationdimerization reaction on heating by “Derivatograph”. Comparison of chemical and physical properties of the complexes with those of the corresponding chromium (III) complexes was made.
Spectral and Magnetic Studies on Bi- and Tri-Nuclear Complexes Derived from Copper(II) Complexes with Tetradentate Schiff Base and One of the Chlorides, Nitrates and Perchlorates of Copper(II), Nickel(II), Cobalt(II) and Zinc(II)
Authors: Kato Michinobu , Muto Yoneichiro , Jonassen Hans B , Imai Kyoko , Tokii Tadashi 
Published: July 2006

Abstract
We have prepared a variety of binuclear and trinuclear complexes of the composition Cu-(TDSB)·MX2 and 2Cu(TDSB)·M(ClO4)2, where Cu(TDSB)=N,N′-ethylenebis(salicylideneiminato)copper(II) or N,N′-1,2-propylenebis(salicylideneiminato)copper(II), and M=Co, Ni, Cu and Zn. A few higher polynuclear species were also prepared. The previously reported empirical rule found in binuclear copper(II) complexes, where the two copper ions are in the same environment, that the “higher energies of d-d bands - lower magnetic moments,” was proved to hold in the binuclear copper complexes of the present study, even though the two copper ions are in different environments. For a series of complexes with M = Cu or other metals, and with X = NO3 or ClO4, it was observed that “d-d bands of Cu(TDSB) apperas at the shortest wavelengths when M = Cu.” For perchlorate complexes, the energy of the d-d band is in the order, Co&lt;Ni&lt;Cu&gt;Zn, the same as the Irving and Williams’ order of complex stability. It can then be generalized that in a hetero-polynuclear complex molecule, the strengthening of the coordinate bonds around one metal ion strengthens the coordinate bonds around the other metal ion or ions.
ESR Studies of Some Copper(II) β-Diketone Chelate Complexes in Heterocyclic Basic Solvents
Authors: Yokoi Hiroshi , Sai Mitsuru , Isobe Taro 
Published: July 2006

Abstract
Three representative copper(II) β-diketone chelate complexes, bis-(ethylacetoacetato)copper-(II), bis-(salicylaldehydato)copper(II), and bis-(acetylacetonato)copper(II), have been investigated by the ESR method in order to estimate their structures in various solvents. The super-hyperfine structures due to the equal coupling of the unpaired electron with two nitrogen atoms were clearly observed for the first two complexes dissolved in pyridine or γ-picoline. The structures of these two complexes in pyridine or γ-picoline could be estimated to be as follows; a new square-planar coordination occurs through two nitrogen atoms of these basic solvent molecules and two oxygen atoms of the four originally-coordinating ligand oxygen atoms, and the other oxygen atoms are coordinated as apical ligand atoms with less strength. On the other hand, the ESR spectra of the latter complex dissolved in pyridine or γ-picoline show a significantly strong ligand field only in the axis normal to the molecular plane; this indicates that the coordination of the basic solvent molecules along the axis normal to the molecular plane occurs.
The Hydrolysis of the Beryllium Ion in Heavy Water
Authors: Kakihana Hidetake , Maeda Masunobu 
Published: July 2006

Abstract
The hydrolysis of Be2+ ion in heavy water containing 3m NaClO4 as an ionic medium was investigated at 25°C by potentiometric titrations, employing a technique of constant-current coulometry. The deuterium-ion concentrations was measured by the use of a commercial glass electrode. The emf data in the range of the total beryllium concentration from 2.5 to 10 mm can be explained on the basis of the following complex formation: Be2(OD)3+, −logβ1,2=3.28±0.04; Be3(OD)33+, −logβ3,3=9.399±0.007; Be(OD)2, −logβ2,1=11.89±0.07. The composition of the species formed in heavy water is the same as that in light water, but the values of the stability constants are smaller in heavy water than in light water.