bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural Effects on the Properties of Nonionic Surfactants. I. The Synthesis and Some Surface Activities of Acetal Type Homogeneous Nonionics
Authors: Kuwamura Tsunehiko , Takahashi Hideo 
Published: July 2006

Abstract
Higher aliphatic aldehydes (C8–C16) were treated in the presence of mineral acid with several pure polyoxyethylene glycols (m : 2–6), to give the corresponding acetals (AG types) with a general formula RCH[O(C2H4-O)mH]2. These AG types are soluble in water, fairly stable in neutral and weakly basic aqueous solutions, and they exhibited the characteristic properties of nonionics. The hydration of the geminal polyoxyethylene (POE) chains are discussed on the basis of the data of unexpectedly low cloud points. Surface tension measurements on the aqueous solutions of AG types indicated that the critical micelle concentration (CMC) value decreases with an increment of oxyethylene units (m), and that the molecular area does not depend so greatly on m and is significantly smaller than that predicted from the data of conventional nonionics (S types) having one hydrophobic and hydro-philic chain each. For the gross effects of AG types, it has been found that the foam stability is considerably low and the dependence of the wetting power for canvas discs on m is larger than that of S types. The results are discussed on the basis of structural characteristics related to the unfavorable hydration and restricted configuration of the geminal POE chains. The acid-catalyzed hydrolysis of AG types in the micellar solution was significantly slower than that of acetaldehyde diethylacetal in water.
Electron Spin Resonance Studies of Bis (acetylacetonato)copper(II) Adsorbed on X-Type Zeolite. II. The Substitution Reaction of Ligands with Pyridine
Authors: Yamada Yoshio 
Published: July 2006

Abstract
The interaction of bis(acetylacetonato)copper(II) (Cu(acac)2) adsorbed on X-type zeolite of the sodium form with pyridine was investigated by means of ESR. When a pyridine vapor was introduced to Cu(acac)2 on the zeolite, the spectral lines of the perpendicular g component for Cu(acac)2 were replaced by those consisting of a superhyperfine structure, which arises from the ligand nitrogen atoms. The observed spectrum was assigned to [Cu(pyridine)4]2+. Such a characteristic substitution reaction of Cu(acac)2 with pyridine was not, however, observed on silica gel nor in ordinary solvents. It is pointed out, on the basis of these results and of the considerations described in a preceding paper, that the reaction involves the following mechanism: the interaction of quasi-π-electrons in Cu(acac)2 with an electrostatic field originating from the cation on the zeolite lowers the stability of Cu(acac)2, and the complex is attacked by two adsorbed pyridine molecules and two pyridinium ions which are formed by the combination with protons on acid sites, resulting in the substitution reaction. In addition, [Cu-(pyridine)4]2+ was produced on other cation-exchanged zeolites and silica-alumina. The substitution reaction was also found when α-, β-, or γ-picoline was used instead of pyridine.
Interaction of Metal Porphyrins with Molecular Oxygen in Solutions
Authors: Yamamoto Kenichi , Kwan Takao 
Published: July 2006

Abstract
The oxidation of divalent metal tetraphenylporphin complexes by molecular oxygen has been investigated in solutions. It was found that the one-electron oxidation of low-spin iron(II) complexes to yield high-spin iron(III) does not take place, while a low-to-low conversion proceeds with ease. It is suggested that the ready oxidation is due to the delocalization of the dπ electrons of iron(II) to the vacant π-orbital of the porphin ligand. Oxidative mechanisms of manganese(II) and cobalt(II) tetraphenylporphins were also discussed.
The Intermolecular Potential of Hydrocarbon Dimers as Examined by the Perturbation Theory Including Exchange Energy in the PPP Approximation
Authors: Fujita Hiroko , Imamura Akira 
Published: July 2006

Abstract
By using the perturbation method, including the exchange energy, the interaction potential curves for the intermolecular distances from 2.0 Å to 6.0 Å of the ethylene dimer, the butadiene dimer, the hexatriene dimer, and the benzene dimer were obtained. The matrix elements were evaluated in the Pariser-Parr-Pople approximation. Reasonable intermolecular potential curves were obtained for all the dimers studied. The analysis of the perturbation energy leads to the conclusion that the induction and dispersion energies and the exchange repulsion energy of the second order in the overlap integral give the potential minimum for the interaction of small molecules, such as ethylene or butadiene dimers, but for large molecules, such as benzene or hexatriene dimers, the exchange repulsion energy of the fourth order in the overlap integral should also be included in order to obtain the potential minimum. An important role of the charge transfer term was suggested for the chemical reaction; this was in agreement with the indications of previous researchers. The calculated depth of the potential minimum and the equilibrium molecular distance are in fairly good agreement with the experimental data.
The Magnetic Properties of Cu3Cl6(C6H7NO)2·2H2O
Authors: Miyoshi Hirokazu , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo 
Published: July 2006

Abstract
From magnetic susceptibility and ESR measurements, it has been confirmed that polybis(μ-(2-picoline N-oxide)-chlorocopper(II)di-μ-chloro)diaquocopper, Cu3Cl6(C6H7NO)2·2H2O, consists of alternating linear chains with diamagnetic Cu2Cl4(C6H7NO)2 units and paramagnetic CuCl2·2H2O units joined by long Cu–Cl bonds. The two copper ions in the Cu2Cl4(C6H7NO)2 unit are coupled together very strongly by antiferromagnetic exchange interaction and occupy almost entirely the diamagnetic singlet state below room temperature. This interpretation is appropriately supported by the observation of a half-field resonance near 1600 Oe in the ESR spectrum of the powdered sample. On the other hand, the copper ion in the CuCl2·2H2O unit isolated magnetically can account for the ESR spectrum due to ΔM=±1 transition and magnetic susceptibility, following the Curie law. The magnetic susceptibility of the dehydrate compound, Cu3Cl6(C6H7NO)2, has also been measured.
The Dehydrogenation of Amines by Molten Metal Catalysts
Authors: Okano Kiyohisa , Saito Yasuo , Ogino Yoshisada 
Published: July 2006

Abstract
In order to investigate the catalytic activity of molten metal, experiments were carried out using the dehydrogenation of n-butylamine, benzylamine, and cyclohexylamine as test reactions. The molten zinc catalyst was thus found to show specially high activities and selectivities in all test reactions. The activity of the molten gallium catalyst for the dehydrogenation of n-butylamine was also considerable. However, the selectivity of this catalyst was somewhat lower than that of the molten zinc catalyst, and considerable amounts of dibutylamine were produced at lower reaction temperatures. The other molten metals were found to be almost inactive. That is, Pb, Cd, Sn, and Bi were inactive, while Tl and In were only slightly active.
Structure of the Vanadium-Potassium Catalyst during the Oxidation of Sulfur Dioxide and the Oxidation Mechanism
Authors: Kato Akio , Tomoda Katsuhiko , Mochida Isao , Seiyama Tetsuro 
Published: July 2006

Abstract
The structure of vanadium-potassium catalyst in gas mixtures of various compositions of SO2, SO3, and O2was investigated at 500, 550, and 600°C to elucidate the mechanism of SO2 oxidation on the catalyst. It was found that in the catalyst 50–70% of V(IV) is in VO2+-form, and the rest of the vanadium forms large vanadium-oxygen networks. It was also found that both the reduction of V(V) with SO2 and oxidation of V(IV) with oxygen are in equilibrium and the desorption of SO3 from the molten catalyst into gas phase seems to be the rate-determining step in SO2 oxidation. On the basis of this mechanism, the reaction rate of SO2 oxidation can be formulated as follows,
dSO3⁄dt=k′(SO3)=kPSO2·PO21⁄2.
For the sake of confirmation, the kinetics of SO2 oxidation (below 10% conversion) over vanadium-potassium catalyst was measured by a flow method at 500, 550, and 600°C over gas compositions of SO2=5∼24% and O2=10∼36%. It was found that the rate expression was correct.
Magnetic Properties of Some Iminoxyl Polyradicals. III. Exchange Interaction in Iminoxyl Biradicals
Authors: Nakajima Akira , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo 
Published: July 2006

Abstract
The EPR spectra of TEMPAD and Sulfite biradicals in a dilute solution have been reasonably interpreted in terms of the variation in the ratio of the intra-molecular exchange interaction to the 14N hyperfine interaction. Comparing these spectra with the theoretical ones, the authors have estimated the intra-molecular exchange interactions as 10.0·A=2×10−2k and 3.0·A=5×10−3k respectively. The magnetic susceptibility of the TEMPAD biradical exhibits a broad maximum at a temperature of 16.5°K, while 50 and 75% TEMPAD diluted in corresponding diamine have no maximum in the temperature range measured. The magnetic susceptibility of the sulfite biradical also shows a broad maximum at 15.0°K, in spite of the weak intra-molecular exchange interaction. These results indicate that the origin of the short-range ordering is the inter-molecular exchange interaction between unpaired electrons in different molecules.
Molecular Structures of Acetyl Chloride and Acetyl Bromide as Determined by Gas Electron Diffraction
Authors: Tsuchiya Shuzo , Kimura Masao 
Published: July 2006

Abstract
The molecular structures of acetyl chloride and acetyl bromide have been investigated by the sector-micro-photometer method of gas-phase electron diffraction. The thermal average distances, rg, and the valence angles, \varphia, have been determined, with estimated limits of error, to be as follows: for acetyl chloride, rg(C=O)=1.187±0.003 Å, rg(C–Cl)=1.798±0.003Å, rg(C–C)=1.508±0.005 Å, \varphia(OCCl)=120.3°±0.6°, \varphia(CCCl)=112.2°±0.09°, and \varphia(CCO)=127.5°±0.9°; and for acetyl bromide, rg(C=O)=1.184±0.004 Å, rg(C–Br)=1.975±0.004 Å, rg(C–C)=1.518±0.008Å, \varphia(OCBr)=120.8°± 0.9°, \varphia(CCBr)=109.5°±1.2°, and \varphia(CCO)=129.7°±1.1°. The C=O distances in these molecules are shorter than those in acetaldehyde and acetone by about 0.02 Å. This may be attributed to the effect of a highly electronegative halogen atom adjacent to the carbonyl group.
Electronic Spectra and Structures of Organic π-Systems. VII. Electronic States of Benzoylium, Acryloylium, and Cinnamoylium Ions
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi 
Published: July 2006

Abstract
The electronic states of benzoylium, acryloylium and cinnamoylium ions have been studied by a semiempirical ASMO LCAO SCF CI method including both π- and \barπ-systems.
The results suggest that the contribution of the canonical formula R−–\overset+CO or R–\overset+CO to the ground state in ketene should be smaller than that in benzoylium, acryloylium or cinnamoylium ion. The longest wavelength singlet-singlet transition of benzoylium or cinnamoylium ion is π–1π as in benzenediazonium ion, and that of acryloylium ion is π–1\barπ as in ketene, diazomethane and diazocyclopentadiene.
The Benzene-photosensitized Decomposition of Carbonyl Sulfide in a Cyclohexane Solution
Authors: Sato Shin , Miyamoto Hiroshi , Hirokami Shun-ichi , Tsunashima Shigeru 
Published: July 2006

Abstract
The decomposition of carbonyl sulfide photosensitized by benzene in the solution of cyclohexane has been investigated at room temperature. The quantum yield of CO formation, φCO, at an infinite concentration of COS was estimated to be 1.0. The COS concentration dependence of φCO corresponded well to that of the quenching efficiency of COS on benzene fluorescence. These results suggest that, of the two possible photosensitization processes:
C6H6(1B2u)+COS→C6H6+CO+S(1D)
and
C6H6(3B1u)+COS→C6H6+CO+S(3P),
the former is responsible for the formation of CO. The very small yield of cyclohexanethiol may be explained by the fact that benzene is an efficient catalyzer for the transition process, S(1D)→S(3P).
Amino Wagging of the tert-Butylamine in Ã Electronic State
Authors: Hirakawa Akiko Y , Miyazaki Hideyuki , Tsuboi Masamichi 
Published: July 2006

Abstract
Ultraviolet absorption spectra of two isotopic t-butylamines, (CH3)3CNH2 and (CH3)3CND2, have been observed in their gaseous state in the spectral region 2000–2500 Å. There is an electronic band, whose 0–0 band peaks are observed respectively at 2351.2 and 2334.9 Å. The vibrational structure of the band, caused by the amino wagging vibration, was analyzed. On the basis of the observed energy levels, the potential function of the excited molecule along the amino wagging coordinate was determined; it is nearly harmonic with a small positive quartic term. The dependence of intensity on the vibrational quantum number and the intensity ratio of the fundamental and the hot bands indicate that the equilibrium structure of the amino group is the same as that of methylamine; the angle between the C–N axis and the HNH plane has been determined to be 51± 4°.
Laser Photolysis Studies on the Formation of Solvated Ion Radicals in the Pyrene–N,N-Dimethylaniline System in Various Solvents
Authors: Taniguchi Yoshio , Nishina Yasuzo , Mataga Noboru 
Published: July 2006

Abstract
Formation of solvated ion radicals in the pyrene-N,N-dimethylaniline (DMA) system (which is a typical one showing heteroexcimer (HE) fluorescence) in various solvents has been studied by means of the laser photolysis and transient photoconductivity as well as transient absorption measurements. Ion radical formation due to the encounter collision between an excited pyrene and DMA in moderately as well as in strongly polar solvents has been established. This result is quite important in explaining the experimentally observed relation between the solvent dependent HE fluorescence quantum yield and decay time.
Copper(II) Chelates of 2,4,6-Heptanetrione and Its Homologues
Authors: Sagara Fumio , Kobayashi Hiroshi , Ueno Keihei 
Published: July 2006

Abstract
Copper(II) chelates of heptane-2,4,6-trione as well as its methylated derivatives such as 3-methylheptane-2,-4,6-trione, 3,5-dimethylheptane-2,4,6-trione, and 2-methoxy-2-heptene-4,6-dione have been synthesized. All the ligands gave 1 : 2 (metal ion: ligand) chelates. The first two ligands gave in addition binuclear 2 : 2 chelates. The fact that a 1 : 2 chelate was relatively easily converted into a 2 : 2 chelate and the conversion occurred more easily with the chelate of the first ligand than with that of the second one was interpreted by the steric effect of the methyl group. The structures of the 1 : 2 and 2 : 2 chelates were discussed on the basis of spectroscopic and other data. Reversible addition of heterocyclic bases to the 2 : 2 copper chelates was observed, and the coordinating structure of pyridine adduct was found to be of a pentacoordinate square pyramid.
Partial Pressures of Strontium and Strontium Oxide over Strontium Oxide Heated on Platinum
Authors: Asano Mitsuru , Yamamoto Yutaka , Sasaki Noriaki , Kubo Kenji 
Published: July 2006

Abstract
A quadrupole mass filter was used to determine the partial pressures of Sr(g) and SrO(g) over strontium oxide heated on a platinum-ribbon filament. The ion currents of 88Sr+ and 88Sr16O+ were measured while the filament temperature was continuously increasing at a heating rate of about 14°C/min; the calculations of the partial pressures were carried out by the integral method for Sr(g) and by the sensitivity-calibration method for SrO(g). The data are represented by:
logPSr(g)(atm)=6.633−\frac2.536×104T
in the temperature range of 1643–1851°K, and by:
logPSrO(g)(atm)=6.707−\frac2.793×104T
in the 1747–1850°K range. From the values of the partial pressures, the dissociation energy of strontium oxide was determined to be D0°(SrO)=96.2±0.9 kcal/mol by the third-law treatment and D0°(SrO)=102±5 kcal/mol by the second-law treatment.
The Apparent Molar Volumes of Tetraalkylammonium Halides in Liquid Sulfur Dioxide
Authors: Uosaki Kohei , Kondo Yasuhiko , Tokura Niichiro 
Published: July 2006

Abstract
The apparent molar volumes, Φv, of tetraalkylammonium halides, R4NX (R=Me, Et, n-Pr, and n-Bu; X=Br− and I−), have been determined in liquid sulfur dioxide at several concentrations, and from these values the apparent molar volumes at an infinit dilution, Φv°, have been obtained for these salt at 25°C. The results indicate that, for all the salts, the Φv vs. \sqrtc curves are almost straight over the concentration ranges studied. The slopes of the plots have large positive values for all the salts in this solvent. In order to study the ion-solvent interaction, the apparent molar volumes of the individual ions at an infinit dilution have been determined from those values by Conway’s method. While the Φv° values of tetraalkylammonium ions are similar to those in other solvents, the Φv° values of bromide and of iodide ions in this solvent are quit small compared with those in other solvents. The results can be explained in terms of a strong anion-solvent interaction in liquid sulfur dioxide resulting from the formation of a charge-transfer complex of the halide ion with sulfur dioxide.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. VII. Syntheses and Electronic Spectra of 1,1′- and 2,2′-Dipyrenylpoly-ynes
Authors: Nakasuji Kazuhiro , Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
1,1′- and 2,2′-Dipyrenylpoly-ynes (In and IIn, n=1–6) have been synthesized. It was found that the bathochromic shift of the longest-wavelength absorption maxima (λL) according to the increase in the number of acetylenic bond (n) can be well expressed by the following formulas:
In:λL=3.7n1.7+430 (nm in toluene)
In:λL=12.6n1.4+327 (nm in toluene)
Linear Conjugated Systems Bearing Aromatic Terminal Groups. VIII. Syntheses and Electronic Spectra of Bis(4-biphenylyl)- and 2,2′-Difluorenylpoly-ynes
Authors: Nakasuji Kazuhiro , Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
In order to get further information on the effect of terminal groups on the spectral regularity of diarylpoly-ynes, we carried out the syntheses of bis(4-biphenylyl)poly-ynes (In, n=1–6) and 2,2′-difluorenylpoly-ynes (IIn, n=1–4 and 6). The bathochromic shift of the longest-wavelength absorption maxima (λL) along with the increase in n was found to be expressed by the following empirical formulas:
In:λL=24.0n1.1+304 (nm in tetrahydrofuran)
IIn:λL=9.0n1.5+350 (nm in tetrahydrofuran)
The spectral behavior of bis(4-biphenylyl)poly-ynes (In) strongly supported the relationship λL∝n in diphenylpoly-ynes.
Asymmetric Reactions. VII. Stereoselectivities in Phenyllithium and Grignard Reactions with Tetrahydrofurfural Derivatives
Authors: Yoshimura Juji , Ohgo Yoshiaki , Ajisaka Katsumi , Konda Yaeko 
Published: July 2006

Abstract
Stereoselectivities in the phenyllithium and phenylmagnesium bromide reactions with tetrahydrofurfural (1), its diacetate (2) and 5,5-dimethyl-(S)-tetrahydrofurfural (3) were examined, in order to clarify the cause of anomalous stereoselectivity of Grignard reactions with N-substituted 2,3-O-isopropylidene-d-glyceraldimine and the carbonyl analogue (giving erythro product predominantly). The presumption that the anomalous stereoselectivity might be caused by coordination ability of magnesium to C3-oxygen, together with C1-oxygen or C1-nitrogen, and C2-oxygen, was solidified from the present results that no stereoselectivity difference was observed between both reactions with substrates having no C3-oxygen. Detailed discussion on the stereoselectivity differences between substrates was also made.
The Microwave Spectrum of Dimethyl Sulfone
Authors: Saito Shuji , Makino Fumio 
Published: July 2006

Abstract
The microwave spectra of normal and 13C-isotopic species of dimethyl sulfone have been investigated, and the rotational constants of both species have been determined. The following r0-structural parameters have been determined: r(C–S)=1.777±0.006Å, r(S–O)=1.431±0.004Å, ∠CSC=103°17′±10′, and ∠OSO=121°1′±15′, assuming that r(C–H)=1.091Å and ∠HCH=109°34′. The variations in the structural parameters among the related alkyl sulfides, alkyl sulfoxides, and alkyl sulfones have been discussed. The dipole moment has been determined to be μ=4.432±0.041 D along the b axis. This value is consistent with the results of a bond-moment calculation based on the dipole moment of dimethyl sulfoxide.
Low-Frequency Raman Spectra and Phase Transition of the 1,2-Dichloroethane Crystal
Authors: Ozora Akira , Nakagawa Tsugito , Ito Mitsuo 
Published: July 2006

Abstract
In order to study the phase transition of 1,2-dichloroethane crystal at 177°K, the low-frequency Raman spectra were measured at various temperatures, and normal coordinate analysis was carried out. It was found that the phase transition is of rotational type in which the librational motion of the molecule about the axis passing through two chlorine atoms of the molecule changes into a nearly free rotation about the same axis.
Studies of Salt Solution Aerosols. VIII. The Effect of Humidity on the Stability of Spray-dried Na2SO4 Aerosol and an Estimate of the Particle Density
Authors: Ueno Yasuo , Sano Isamu 
Published: July 2006

Abstract
The aerosols obtained by spraying an aqueous Na2SO4 solution of concentrations ranging from 0.1 to 10% by weight were dried by a furnace at 200 to 800°C and were then subjected to stirred aging at room temperature in an atmosphere of 90% relative humidity or less; the variations in both mass concentration and particle size were then measured with the lapse of time.
By employing the results thus obtained and by making some assumptions, the density of the particle in dried aerosols was calculated to be several tenths of one gram per cc, which is smaller by a factor of 3 to 4.5 than the bulk density of solid Na2SO4; further, the amount of water which the dried particle might hold if kept in a humidified atmosphere was estimated, with the finding that the density of a particle would decrease with increase in its water content; for example, the density of the particle with composition of Na2SO4·10H2O would be 0.32 g/cc, smaller by a factor of 4 to 5 than the bulk density. In addition, the influence of water vapor on the stability of the dried aerosols was studied; it was found that the higher the humidity, the greater the rate of coagulation.
Hydrogen Exchange Reactions between Olefins or an Olefin and Molecular Hydrogen over Alumina Studied by Microwave Spectroscopy
Authors: Sakurai Yuzo , Onishi Takaharu , Tamaru Kenzi 
Published: July 2006

Abstract
The exchange reaction between propylene and deuterium was studied over alumina. The rate of the reaction was expressed by Vex=k[PD2]0.5[PPro]0.0. In the initial stages of the reaction the cis- and trans-1 -d1 species of propylene were the only products of the exchange reaction, but the concentration of the 3-d1 species increased continuously as the reaction progressed. The activation energy for the exchange reaction was about 8.2 kcal/mol.
Propylene-cis-d1 was reacted over alumina, and the variation in the deuterium distribution of the propylene was followed by microwave spectroscopy. Isotope scrambling and “double-bond migration” occurred to considerable extents, while cis-trans equilibration between the two C1 hydrogen positions proceeded even faster. In the reaction of propylene-3-d1 the isotope mixing and “double-bond migration” were considerably slower than those of the cis-1-d1 species. Cis- and trans-1-d1 species were formed in equal amounts. The possible mechanism of these reactions is discussed on the basis of the results obtained.