bluuebunny/crossref_metadata_2025 huggingface dataset:
Properties of Water Solubilized in Reversed Micellar Systems of Dodecylammonium Propionate in Nonpolar Solvents
Authors: Sen\={o} Manabu , Araki Koji , Shiraishi Shinsaku
Published: July 2006

The properties of the reversed micelles of dodecylammonium propionate (DAP) and of solubilized water were examined for systems with hexane, chloroform and benzene as a nonpolar component. The aggregation number of DAP, the conductivity, the heat of solution of water, IR and NMR spectra, and near infrared spectra of solubilized water were measured. From the results the properties of the reversed micellar system were analyzed, the following conclusion being obtained. The aggregation state of DAP is scarcely affected by the addition of water. Water is first dispersed in the nonpolar organic phase, and then solubilized in the cores of the reversed micelles. The former is free or weakly bonded water, while the latter is bonded water like that in the bulk phase. The catalytic effect of DAP reversed micellar system is discussed.
The Microwave Spectrum of Thiirane in Excited Vibrational States
Authors: Hirose Chiaki , Okiye Kazuhiro , Maeda Shiro
Published: July 2006

The microwave spectra in the ground and five low-lying vibrational states of 12C2H432S and in the ground state of 12C13CH432S and 12C2H434S have been assigned to high-J transitions. The rotational and centrifugal distortion constants were derived. Four of the five vibrational states were found to be in Coriolis interaction in pairs; one of the pairs was identified as the symmetric and antisymmetric ring deformation modes, ν5(A1) and ν12(B1), but another pair was unexplicable from any of the previously reported vibrational assignments. The infrared and Raman spectra in the liquid and gas phases were examined, and the latter pair of vibrations was interpreted as ν14(B2) at 945 cm−1 and ν8(A2) at about 970 cm−1. This novel assignment of ν8 around 970 cm−1 was based on not only the results of microwave spectroscopy, but also on the observation of an unsymmetric band contour in the infrared spectrum of the gaseous sample.
A Comparison of the Primary Processes of the Radiolyses Induced by α-, β-, and γ-Rays
Authors: Sato Shin , Kowari Ken-ichi , Okazaki Kiyoshi
Published: July 2006

By using the cross sections derived by the binary encounter collision theory and the assumption of a continuous slowing down, the G-values for the ionization and excitation of helium gas irradiated by α-, β-, and γ-rays have been calculated. In the radiolysis by high-energy electrons, the G-values started to decrease at an incident electron energy of about 103 eV with a decrease in the energy. Calculation showed that, if the radiation energy is extremely high, the G-values are independent of the kind of radiation. In the radiolysis induced by α-particles, the ratio of the yield resulting from the direct interaction with α-particles to that due to the secondary electrons was calculated as a function of the energy of the incident α-particles. When the energy was 8 MeV, the ratio for ionization was calculated to be 1.31.
A Photoelectron Spectroscopic Study of Thioformamide
Authors: Kimura Katsumi , Katsumata Shunji , Ishiguro Takahiko , Hirakawa Akiko Y , Tsuboi Masamichi
Published: July 2006

The He I photoelectron spectrum of thioformamide (HCSNH2) has been measured. On the basis of spectral features, CNDO/2 calculations, and sum rule considerations, the following assignments have been concluded. 1) Six ionization bands appearing below 17 eV correspond to six-p-type MOs and two bands in the region 17–20 eV correspond to s-type MOs. 2) The first ionization band is attributed to the highest occupied (in-plane) MO constructed mainly from the sulfur lone pair which is mixed to some extent with the σCN orbital. 3) The second and fourth bands are due to the out-of-plane MOs, mainly corresponding to the nitrogen lone pair and the πcs orbital, respectively. 4) The remaining p-type bands may be interpreted in terms of σCS, σCN, and πNH2 (pseudo pi) orbitals.
The Crystal and Molecular Structure of N-Carboxy Anhydride of Glycine
Authors: Kanazawa Hitoshi , Matsuura Yoshiki , Tanaka Nobuo , Kakudo Masao , Komoto Tadashi , Kawai Tohru
Published: July 2006

The crystal and molecular structure of N-carboxy anhydride(NCA) of glycine was determined from three-dimensional X-ray diffraction data. The crystals of glycine-NCA are monoclinic with space group C2/c and Z=8; the cell dimensions are a=9.298(2), b=5.156(2), c=16.900(4) Å and β=107.88(2)°. A pair of molecules forms the dimer structure around a center of symmetry, with two N(1)–H(1)···O(1′) hydrogen bonds in the crystals.
Dielectric Relaxation Mechanism in Some Substituted Phenones
Authors: Sahni Neera , Shukla J P , Saxena M C
Published: July 2006

Dielectric constants and losses at microwave frequency as well as static dielectric constants and refractive indices have been measured for o-methylacetophenone, m-methylacetophenone, o-hydroxybutyrophenone, 2′,4′-dihydroxyacetophenone and 2′,4′-dihydroxypropiophenone in dilute solutions of 1,4-dioxane. These values are used to calculate the dielectric relaxation times, distribution parameters, dipole moments and activation energies of the molecules. The results have been discussed in terms of the molecular motion of the system in the medium. Comparatively higher relaxation times and their variations irrespective of the molecular size, have been attributed to the intermolecular hydrogen bonding between the solvent and solute molecules.
The Electronic Spectra of α,ω-Di-1- and α,ω-Di-2-naphthylpolyenes in Solution and in Solid State
Authors: Mandal Krishnagopal , Misra T N
Published: July 2006

The electronic absorption spectra of α,ω-di-1- and α,ω-di-2-naphthylpolyenes have been studied in solution and in the crystalline state. Both polyenes have four distinct electronic band systems. The spectral properties indicate that the terminal naphthyl group reduces the symmetry of the short-chained polyene molecules whereas long naphthylpolyenes retain the usual conjugated polyene symmetry of C2h. A plot of λmax2-n gives a straight line and a nearly all-trans form seems to be retained by the polyene chain. Unlike that in some conjugated polyenes a good overlap between the first absorption band and the highest energy emission band is observed. This suggests that there is no low-lying forbidden state in these polyenes. Some of the absorption bands of naphthylpolyene crystal could be explained in terms of factor group split components. Two extra bands observed in α,ω-di-2-naphthylpolyenes seem to be related to naphthalene transitions.
Rotational Isomerism in β-Diketone cis and trans Enol Ethers. An IR and PMR Study
Authors: Dabrowski Janusz , Tencer Michal
Published: July 2006

The cis (Z) isomers of β-alkoxy-α,β-unsaturated ketones, R1COCH=CR2OR3, have been shown by IR spectra to exist as a mixture of s-cis (ZZ) and s-trans (ZE) rotamers, with the equilibrium shifting towards the former upon increasing the steric requirements of the R1 substituent. The trans (E) isomers have uniformly the s-cis (EZ) structure. O-s-trans (or non-planar) and O-s-cis conformations due to rotation around the Csp2–O bond have been proposed for the Z and E isomers, respectively. Based on known structures, a rationalization of the rule governing the chemical shifts of R1 and R2 protons, called here the “ene-one cross shielding rule”, has been offered.
New Red Pentaamminenitrosylcobalt(III) Complexes Obtained by the Reaction of a Cobalt(II)-ammoniacal Solution with Nitrogen Oxide
Authors: Miki Eiichi , Ishimori Tatsujiro
Published: July 2006

New Red Pentaamminenitrosylcobalt(III) chloride and nitrate, [Co2(N2O2)(NH3)10]Cl4·4H2O and [Co2(N2O2)(NH3)10](NO3)4·2H2O were prepared by the reaction of NO at ca. 0 °C with a cobalt(II)-ammoniacal solution which had been exposed to air for 20 h at ca. 20 °C. Data of the new red salts were compared with those of the red salt [Co2(N2O2)(NH3)10](NO3)4·H2O prepared by Sand and Genssler. The new red salt may be considered to be a linkage isomer of the red salt, a binuclear complex in which two of the Co(NH3)5 groups are bridged through a dimer of nitrosyl group, N–O–O–N2− ion.
Phase Equilibria in Fe–Fe2O3–Ln2O3 (Ln=Sm and Er) Systems at 1200 °C
Authors: Kitayama Kenzo , Katsura Takashi
Published: July 2006

Phase equilibria in Fe–Fe2O3–Ln2O3 (Ln=Sm and Er) systems were established at 1200 °C. In the Fe–Fe2O3–Sm2O3 system, perovskite, garnet, magnetite, wustite, and metallic iron were stable, while in the Fe–Fe2O3–Er2O3 system, the ErFe2O4 phase appeared in addition to the other five phases. On the basis of the phase equilibria, the Gibbs free energy for the reaction of LnFeO3, Ln3Fe5O12, and ErFe2O4 from Ln2O3, metallic iron, and oxygen was determined to be as follows: SmFeO3 −64.1±0.1 kcal, Sm3Fe5O12 −298.5±0.5 kcal, ErFe2O4 −100.8±0.1 kcal, ErFeO3 −59.7±0.3 kcal, and Er3Fe5O12 −286.2±0.7 kcal.
Kinetic Studies in the Selective Formation of Thymol from m-Cresol and Propylene in the Liquid Phase over “FeSO4–Al2O3” Catalysts
Authors: Yamanaka Tohr , Nakata Fumio
Published: July 2006

The kinetics in a liquid-phase isopropylation of m-cresol (I) with 9–25 kg/cm2 of propylene (VI) was studied at 240–280 °C over catalysts prepared from FeSO4 and γ-Al2O3. The rates of the formation of thymol (II) and 4-isopropyl-5-methylphenol (III) and the subsequent isopropylations of II and III were fitted to an irreversible, firstorder rate equation with respect to each starting material. All of the rate constants were roughly proportional to the 1.5th power of the surface acidity of 1≤H0≤3 of catalysts and the 2.2nd power of the pressure of VI. The apparent activation energies were 22 kcal/mol for Steps I→II, II→2,4-diisopropyl-5-methylphenol (V), and III→V and 6.5 kcal/mol for Steps I→III and II→2,6-diisopropyl-5-methylphenol (IV).
Generation of Ketocarbenoid by α-Elimination of ω,ω-Dibromoacetophenone with Copper, and Trapping by Cycloaddition to Olefins
Authors: Kawabata Nariyoshi , Fujii Tetsuya , Naka Michiharu , Yamashita Shinzo
Published: July 2006

Ketocarbenoid was generated by the reaction of ω,ω-dibromoacetophenone with copper in aromatic hydrocarbon, and was trapped by cycloaddition to olefins. This is the first example of cyclopropanation of olefins by formally divalent carbon intermediate without use of diazoketones.
The Analytical Application of Oleophilic Quaternary Ammonium Salts. X. The Extraction of the Niobium–Pyrocatechol Violet-Tridodecylethylammonium Ternary Complex
Authors: Shijo Yoshio
Published: July 2006

The formation and extraction of the niobium–Pyrocatechol Violet–tridodecylethylammonium ternary complex have been examined. The optimal pH for the extraction is 4–5. The molar absorptivity of the complex is 4.4×104 cm−1·mol−1·l at 553 nm. Its composition is estimated to be (Remark: Graphics omitted.).
The Electrochemical Behavior of Mononitrophenyltrimethylsilanes and 2,4-Dinitrophenyltrimethylsilane
Authors: Watanabe Hamao , Aoki Masafumi , Matsumoto Hideyuki , Nagai Yoichiro , Sato Takeo
Published: July 2006

The CV data for o-, m-, and p-nitrophenyltrimethylsilanes and 2,4-dinitrophenyltrimethylsilane revealed that the former three show Epe slightly more anodic than the corresponding nitrotoluenes; the latter shows a third peak (O3) together with two successive reversible couples, while the methyl analogue exhibits no peak corresponding to O3, but shows extremely weak O1. The behavior of these silyl compounds are interpreted in terms of less electron-donating nature of trimethylsilyl group and (p-d)π bonding between the siliicon and benzene ring.
Synthesis and Electrical Conductivity of Phosphorus-Nitrogen Compounds. V. Synthesis and Electrical Resistivity of Poly[bis(amino)phosphazenes]
Authors: Hayashi Takashi , Saito Hajime
Published: July 2006

Three new poly [bis(amino)phosphazenes] of formulas [NP(NHC6H13)2]n, [NP(NHCH2CHCH2)2]n, and [NP(NHCH2C6H5)2]n have been synthesized by direct aminolysis of (NPCl2)n. The electrical resistivity and thermal stability of a series of poly[bis(amino)phoshazenes], (NPR2) (R: amino group), have been examined. Most polymers showed an increase in resistance with time to an equilibrium value, possibly due to space charge effects, allowance for this conductivity being ohmic up to 500(V/cm). The aliphatic amino derivatives have a lower resistivity and a lower ΔE value than the aromatic amino derivatives. The resistivity of the poly [bis(amino)phosphazenes] was found to decrease in the order, R : NHC2H5>NHC3H7>NHC4H9>NHC6H13>>N(CH3)2. This seems to be predominantly due to the nature of an inductive electron supply of amino side groups. In some polymers the change of energy gap, ΔE, was observed in the range 70–90 °C. The ΔE value was usually lower in the low temperature region than in the high temperature region. All the polymers were found to decompose at about 200 °C, losing the amino side group.
The Crystal and Molecular Structures of trans-Dichlorobis(dimethyl-neomenthylphosphine)nickel(II), an Asymmetric Hydrosilylation Catalyst of Olefin
Authors: Kan Kojiro , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The molecular structure of [NiCl2{Me2neoMen)P}2], an asymmetric hydrosilylation catalyst of olefin was determined by means of X-ray diffraction. This complex forms dark red monoclinic crystals; a=9.527(1), b=8.048(2), c=19.461(3) Å, β=99.12(1)°, space group P21 with Z=2. The structure, determined by the heavy-atom method, has been refined anisotropically by a least-squares procedure to R=0.099 for 3023 non-zero reflections. The geometry around the nickel atom is trans-square planar [Ni–Cl 2.151(5) and 2.175(6) Å, Ni–P 2.239(5) and 2.230(5) Å], Two neomenthyl groups are located above and below the co-ordination plane.
Photoemission and Solvation Free Energies of Electrons in Polar Solvents
Authors: Yamashita Kazuo , Imai Hideo
Published: July 2006

The red limit potential of electron photoemission was measured in various polar solvents, and the apparent solvation free energies of the electrons were estimated. The energy state and transformation of photoemitted electrons in solution were discussed as regards the role of dry or damp electrons as an intermediate species. A proportionality between the intermediate solvation free energy and the energy quantum of the optical absorption band maximum of solvated electron in various polar solvents is pointed out.
Studies on 5-8 Fused Ring Compounds. I. Halogenation of 4,4-Dimethylbicyclo[6.3.0]undecane-2,6-dione
Authors: Umehara Misao , Hishida Shinzaburo , Fujieda Kunimi , Sasaki Hirooki
Published: July 2006

Bromination and chlorination of 4,4-dimethylbicyclo[6.3.0]undecane-2,6-dione (2) with pyridinium bromide perbromide and sulfuryl chloride gave several α-halo-diones. The substituted positions and the stereochemistry of the halogen atoms have been assigned on the basis of their dehydrohalogenation and spectral data. The chlorination of 2 also gave a tricyclic dione (8) containing a cyclopropane ring. The structure of 8 was determined by means of 13C-NMR, as well as other types of spectroscopy. Dehydrochlorination of 7 gave a 5H-benzocyclo-heptene derivative (18).
A Three-Component Reaction of Isocyanides with Halogens and Cyclic Ethers
Authors: Yamazaki Takeshi , Wada Yasuo , Tanimoto Shigeo , Okano Masaya
Published: July 2006

In the presence of a Lewis-acid catalyst, such as HgCl2 or ZnCl2, cyclohexyl isocyanide reacted with chlorine and tetrahydrofuran to give, after hydrolysis, 4-chlorobutyl cyclohexylcarbamate in a fair yield. When one of the reactants was replaced by another isocyanide, bromine, or another cyclic ether, the reactions proceeded similarly, but the corresponding carbamate yields were rather poor.
Oxidative Addition of α-Bromo Esters to Tetrakis(isocyanide) Rhodium(I) Complexes. Evidence for a Chain Mechanism
Authors: Otsuka Sei , Ataka Kikuo
Published: July 2006

The oxidative additions of chiral alkyl halides, (S)-(−)-ethyl α-bromopropionate [α]d−18.9° (c 3.3, CHCl3) and (S)-(+)-ethyl α-phenylbromoacetate [α]d+56.4° (c 1.6, C2H5OH) to [RH(R′NC)4]+ (R′=t-Bu, p-CH3C6H4) produced the corresponding adducts, trans-[RhBr(R)(R′NC)4]+ (R=CH3CHCO2Et, PhCHCO2Et), which were well characterized by elemental analysis, IR and 1H NMR spectra. These adducts were found optically inactive, a fact which precludes a concerted mechanism. The reaction of C6H5CHBrCO2C2H5 with [Rh(t-BuNC)4]+ commenced immediately in the absence of light. Taking this system as a typical example, the rate was studied by the stopped-flow method to find a rate equation, R=k[Rh(I)]2[RX]. The relative rate of addition of p-XC6H4CHBrCO2C2H5 to [Rh(t-BuNC)4]+ decreases in an order of Cl>H>CH3 for X. The addition of C6H5CHBrCO2C2H5 to [Rh(p-CH3C6H4NC)4]+ in the dark proceeds only slowly, but rapidly under a low energy photo-irradiation (440 nm) with a large quantum yield (φ 4.8). The addition of CH3CHBrCO2C2H5 requires photo-initiation. The optical activity of (S)-(−)-CH3CHBrCO2C2H5 was completely lost before the oxidative addition commenced. The rate of decrease in optical activity of the system (S)-(−)-C6H5CHBrCO2C2H5/[Rh(t-BuNC)4]+ exhibited approximate second order kinetic behavior, and quantitative racemization took place prior to the completion of the oxidative addition. A chain mechanism appears to be consistent with all these results. Alternate mechanisms are also discussed in the light of the present results.
Effect of Hydrogen Bonding on the Rotational Barriers of Partial Double Bonds. III. 2,6-Dihydroxyaryl Carbonyl Compounds
Authors: Hirota Minoru , Suzuki Toshio , Abe Kazuhisa
Published: July 2006

Activation parameters of internal rotation around Car–Ccarbonyl bonds are determined by means of DNMR spectroscopy for 2,6-dihydroxybezaldehyde and some 2,6-dihydroxybenzoates. The ΔG\eweq and ΔH\eweq of these compounds are ca. 10 kJ mol−1 higher than those for the reference compounds void of ortho-hydroxyl groups, and the excess stabilization is attributed to the contribution of the intramolecular hydrogen bonding. The intramolecular hydrogen bonding in these compounds were discussed on the basis of their infrared spectra in the νOH region.
Synthesis of Ferrocene–Phenol Resins and Liberation of Iron Particles by Pyrolysis
Authors: Omori Mamoru , Nagashima Kazuo , Yajima Seishi
Published: July 2006

Ferrocene–phenol resin was synthesized from 1-ferrocenylethanol, phenol, and formaldehyde in the presence of an ammonia catalyst. The resin structure was elucidated by chemical and infrared analyses and then confirmed by micro Vickers hardness measurements. To liberate iron atoms from ferrocene skeletons, the resin was pyrolyzed in vacuo at 400 °C. The properties of the iron dispersed in a glasslike carbon matrix were investigated by magnetic susceptibility measurements, ESR, and Mössbauer spectroscopy. The iron atoms coagulated into ferromagnetic iron particles in the glasslike carbon matrix. This coagulation is discussed in connection with the resin structure.
A New Method for the Preparation of δ-Alkoxy-α,β-unsaturated Aldehydes and Polyenals
Authors: Ishida Akihiko , Mukaiyama Teruaki
Published: July 2006

Dienoxysilanes (2) react with acetals in the presence of TiCl4 and also in the coexistence of TiCl4 and Ti(OiPr)4 to give δ-alkoxy-α,β-unsaturated aldehydes (3–5) in good yields. In the presence of 1,8-diazabicyclo[5.4.0] undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene and molecular sieves 3A or 4A, the elimination reaction of δ-alkoxyl group of α,β-unsaturated aldehydes (3–5) proceeds smoothly to afford the corresponding polyenals in good yields.
Branched-chain Sugars. IX. Reaction of 3,6-Anhydro-1,2-O-isopropylidene-α-d-ribo-hexofuranos-3-ulose with Nitromethane or Hydrogen Cyanide
Authors: Sato Ken-ichi , Yoshimura Juji , Shin Chung-gi
Published: July 2006

3,6-Anhydro-1,2-O-isopropylidene-α-d-ribo-hexofuranos-3-ulose (2) was converted into 5,6-di-O-acetyl-1, 2-O-isopropylidene-α-d-ribo-hexofuranos-3-ulose (5) by the protection of the carbonyl function with hydroxylamine, followed by acetylation and removal of the protecting group with chromium(II) acetate. Nitromethane condensation of 2 and 5 at room temperature gave the corresponding 3-nitromethyl derivatives having d-gluco- and d-allo-configuration, respectively. The difference in the stereoselectivity was explained by the easiness of isomerization of the initial product to thermodynamically stable epimer, because the reaction temperature was essential to control the selectivity in the same reaction of 1,2 : 5,6-di-O-isopropylidene-α-d-ribo-hexofuranos-3-ulose. Reaction of 2 with hydrogen cyanide in dry pyridine followed by acetylation gave the corresponding 3,5,6-tri-O-acetyl-3-cyano derivative of d-allo-type, whereas, the reaction in water gave instantly 3-(hydroxycarbonimidoyl)-1,2-O-isopropylidene-α-d-allofuranose 3′,5-lactone, by the participation of the C5-hydroxyl group.
Adsorption of Benzoic Acid on a Mercury Electrode
Authors: Taniguchi Isao , Machida Koji , Sato Norio , Sekine Taro
Published: July 2006

The differential capacity and the surface tension at the electrode-electrolyte interface of a dropping-mercury electrode were measured in 0.5 M H2SO4 and 0.5 M Na2SO4 solutions for various concentrations of benzoic acid. On the basis of the Frumkin-Damaskin theory, the adsorption of benzoic acid on mercury was studied in the acid solution, and the parameters involved in the F-D theory were determined: A=1.6 μJ cm−2 (Γm=6.5×10−10 mol cm−2), B0=597 l mol−1, a=−0.35–2.5 E/V, and C′=5.95 μF cm−2. The experimental values of the capacity and the surface tension are in good agreement with the theoretical values calculated by using the parameters obtained. The absence of an anodic maximum in the capacity-potential curve in the presence of benzoic acid was determined to be associated with a strong repulsive force between the adsorbed molecules. The value obtained for the maximum surface excess of benzoic acid is explained in terms of adsorption of the acid molecules for a vertical orientation on the electrode surface. This conclusion was supported by comparing the B0 value for benzoic acid with those for phenol and aniline. The adsorption of benzoic acid in neutral solutions is also discussed.
Interaction between Aromatics and Zinc Chloride in the Molten State. The Formation of σ-Complexes and Radicals
Authors: Morita Mikio , Hirosawa Kunio , Sato Toshio
Published: July 2006

The electronic absorption spectra of naphthalene, anthracene, and naphthacene in dried, molten zinc chloride were measured and found to be almost the same as those of aromatics–aluminum chloride complexes in the solid state. ESR measurements were also made; they confirmed the presence of radicals. From these results, it was concluded that the aromatics reacted with molten zinc chloride to form EDA-complexes, i. e., σ-complexes and cation radicals.
A Method for the Preparation of Potassium Hexafluorovanadate(III) and Its Polymorphic Transitions
Authors: K\={o}yama K\={o}ichir\={o} , Hashimoto Yasuhiko
Published: July 2006

In order to determine the best conditions for the preparation of potassium hexafluorovanadate(III), the reaction of V2O3 with KHF2 was studied by means of thermogravimetric analysis, differential thermal analysis and X-ray diffraction analysis. The reaction begins at about 225 °C and terminates at about 300 °C and the decomposition of excess KHF2 terminates at from 300 to 450 °C, depending on the amount of the mixture of V2O3 and KHF2. Potassium hexanuorovanadate(III) is stable in air up to about 300 °C and is oxidized at temperatures higher than 300 °C. Potassium hexanuorovanadate(III) has four polymorphic forms, and the transition points are 158, 200, and 218 °C. The transition from δ to γ or from γ to β on cooling is hindered by adding a small amount of sodium ion.
A Note on the Rates of Complex Formation of Indium(III) with Murexide and the Decomposition of Murexide in the Presence of Indium(III)
Authors: Ohtani Yoshimi , Yagihashi Shin-ichi , Fujimoto Masatoshi
Published: July 2006

Kinetics of the complex formation between In(III) and murexide was studied by means of the temperature-jump method and the rate of decomposition of the ligand in acid nitrate media. The complex formation of InOH2+ with murexide is about 10 times faster than that of In3+. The stability constants indirectly obtained from the decomposition rate of murexide coincide with those from direct stopped-flow measurements.
Photoreaction of Ferrocene with Some Acetylene Derivatives
Authors: Watanabe Haruo , Ito Kazuo , Nakanishi Fumio , Akiyama Takeo , Sugimori Akira
Published: July 2006

The UV-irradiation of ferrocene and dimethyl acetylenedicarboxylate in acetic acid–water solution afforded dimethyl ferrocenylmaleate and dimethyl ferrocenylfumarate in 40 and 5% yield, respectively. Methyl 3-carbamoylpropiolate, dicyanoacetylene, and methyl propiolate were also reactive and the corresponding substituted ferrocenes were obtained. The reaction can be considered to proceed via the excitation of the charge transfer complex between ferrocene and acetylene derivatives.
The Elimination Reaction of Chlorobutane over Some Molten Salts
Authors: Kikkawa Sh\={o}ichi , Nomura Masakatsu , Ikeuchi Takashi
Published: July 2006

The elimination reactions of hydrogen chloride from 1-chlorobutane and 2-chlorobutane over molten salts (ZnCl2, SnCl2, CuCl melts) have been studied by using both a microreactor and a conventional flow reactor. The preferential formation of cis-2-butene in the reaction of 2-chlorobutane can be explained in terms of the stereochemistry of the surface-adsorbed carbonium ion.
Diorganostannylenes. II. Photolytic Reaction of Diphenyltin with Alkyl Halides
Authors: Kobayashi Kazuhiko , Kunô Kazuko , Kawanisi Mituyosi , Kozima Sinpei
Published: July 2006

Photolysis of diphenyltin polymer, (Ph2Sn)m, afforded diphenylstannylene, Ph2Sn:, which was captured by alkyl halides, R′X, to give the insertion products, Ph2R′SnX. The reactivity of Ph2Sn: was found to be lower than that of dibutylstannylene, Bu2Sn:.
Photoreduction of Quinones. I. One-electron Transfer to p-Benzoquinone in Ethanol Studied by ESR during Continuous Photolysis
Authors: Kambara Yoshihiko , Yoshida Hiroshi
Published: July 2006

Electron spin resonance was examined during the continuous photolysis of a flowing solution of p-benzoquinone in ethanol at room temperature. It was found that both semiquinone anions and semiquinone radicals were generated, but their relative yields changed depending on the experimental conditions. The semiquinone anion was generated in a comparatively high yield at low concentrations of p-benzoquinone and at high flowing rates. Its formation was, however, quenched by the addition of acetic acid without transformation to the semiquinone radical. The semiquinone radical was generated efficiently at high p-benzoquinone concentrations and at low flowing rates. Its formation was enhanced by the addition of hydroquinone. These results, as well as the previous results on the effect of the wavelength of light, indicate, in contrast with the currently accepted view, that there is effectively no equilibrium in ethanol between the semiquinone radical and the semiquinone anion under the present experimental conditions, and that the latter is formed by a photoinduced one-electron transfer from solvent to p-benzoquinone. The semiquinone radical seems to arise from the hydrogen abstraction of excited p-benzoquinone from the hydroquinone formed as a product during photolysis.
Magnetic Properties and Low-Field ESR of Organic Free Radicals, Monochloroporphyrexide and Porphyrexide
Authors: Yoshioka Toshio
Published: July 2006

The static magnetic susceptibility, and ESR and proton NMR spectra of powder samples of monochloroporphyrexide were measured above 1 K and compared with those of porphyrexide. A broad maximum in the static susceptibility of monochloroporphyrexide, indicating an antiferromagnetic interaction, appeared at 22.5 K. The relative susceptibilities of the two radicals obtained from the ESR signal intensities and the proton NMR shifts agree qualitatively with the static susceptibilities. In the low-field ESR spectra (135 MHz) of each radical, broadening of the g=2 absorption line and distinct appearance of the g=4 absorption line were found in the temperature region below Tm, the temperature at which the susceptibility is maximum. The anisotropy of the g-value was estimated from Q-band ESR spectra. Furthermore, the unpaired electron-spin distribution over the ring was estimated from the X-band ESR and the proton NMR spectra. The results are interpreted assuming that the magnetic behavior of the two radicals is due to alternating antiferromagnetic Heisenberg linear chains with alternating parameters, a=0.4 and a=0.6, respectively.
The Raman Spectra of Solid and Liquid Tetramethylsilane
Authors: Shinoda Takako
Published: July 2006

Laser Raman spectra of tetramethylsilane in its three crystalline forms and in the liquid state have been observed for the lattice and intramolecular vibrational regions. The bands due to lattice vibrations increase as the transitions from α to β and to γ occur. The spectra of the β and γ forms exhibit crystal-field splittings of intramolecular bands. The observed spectra suggest that the β and γ forms are isomorphous with each other and the α form has a higher symmetry.
Large-Area (600 mm2) Bimolecular Film in Aqueous Solutions. The Effect of an Amine–Ni2+ Complex on the Stability of cis-9-Octadecenylamine Bimolecular Film
Authors: Yoshida Tadayoshi , Okuyama Masataka , Itoh Takahiro
Published: July 2006

A large, planar, bimolecular film (bilayer, 600 mm2) of cis-9-octadecenylamine (oleylamine) was found to be formed in an NiCl2 solution. From the effect of the added metal ions on the proton magnetic resonance spectrum of octadecenylamine, it appears that the complex between the octadecenylamine molecule and the metal ion increases the stability of the bilayer. The thickness of the bilayer depended strongly on the kind of solvent in the filmforming solution. When decane, a normal alkane solvent, was used, the thickness of the bilayer was greatest (4.6 nm), and the temperature effect was smallest. The experimental results are explained in terms of (i) the influence of the solvent on the conformation of the octadecenyl chain and (ii) the amount of solvent remaining in the film.
A CNDO-type MO Method of the Third Transition Metal Complexes and the Electronic Structure of Methylmercury(II) Halides
Authors: Sakaki Shigeyoshi , Hagiwara Nobuo , Iwasaki Noriko , Ohyoshi Akira
Published: July 2006

The parameters of a CNDO-type SCF-MO method are determined for some 5d transition metal complexes such as IrCl63−, AuCl4−, and HgCl42− by comparing the calculated transition energies of these complexes with their experimental values. MO calculations with these established parameters are also carried out for IrBr63−, AuBr4−, HgX42−, HgX2, and CH3HgX (X=Cl, Br, and I). The transition energies and assignments obtained from MO calculations are in fair agreement with experimental ones, with a few exceptions. This MO method gives successful results for the electron density and the bond strength: (1) a linear relation is obtained between the calculated and observed net charges on the Hg atom of HgX2 and CH3HgX, and (2) similar linear relations are obtained between the bond index EM–X values and the stretching force constant fM–X and between the EHg–C value and the fHg–C. Some discussion is presented for the Hg–C bonding character of the CH3HgX; the Hg–C bond is mainly contributed from the covalent interaction of the 6s and 6p orbitals of the Hg atom with the 2s and 2p orbitals of the C atom. The contributions of the Hg 5d orbitals and the electrostatic interaction are rather small.
Studies on Mixed Chelates. VI. Mixed Copper(II) Chelates with N,N,N′,N′-Tetraethylethylenediamine and Various β-Diketones
Authors: Fukuda Yutaka , Miura Yukiko , Sone Kozo
Published: July 2006

Ten new mixed copper(II) chelates containing N,N,N′,N′-tetraethylethylenediamine and various β-diketones were prepared and the cause of the large variations of νmax values observed in the visible absorption spectra of their organic solutions was discussed in comparison with similar variations of the corresponding tetramethyl chelates.
Conductance of Some High Valence Type Electrolytes in Mixed Solvents. II. Conductance of Pentaamminenitrocobalt(III) and Tris(1,10-phenanthroline)iron(II) Sulfates in Water–Ethylene Glycol Mixtures at 25 °C
Authors: Kubota Eiji , Yokoi Masatoki
Published: July 2006

Conductance data are reported for dilute solutions of pentaamminenitrocobalt(III) sulfate, [Co(NO2)(NH3)5]SO4, and tris(1,10-phenanthroline)iron(II) sulfate, [Fe(phen)3]SO4 in water–ethylene glycol mixed solvents at 25 °C. The conductance data were analyzed in terms of the 1957 Fuoss-Onsager and Fuoss-Hsia equations. While the application of the 1957 Fuoss-Onsager equation to [Fe(phen)3]SO4 data suggested a complete dissociation of the salt over the entire range of solvent compositions, the Fuoss-Hsia equation fitted the data better and yielded KA values which are in accord with the ion association theories. [Co(NO2)(NH3)5]SO4 had a higher association constant in the range of solvent composition studied (0 to 40% ethylene glycol) than the predictions of the ion association theories.
ESR of Hot Ions: Low Spin Pt(III) Complex Ions Produced by γ-Irradiation
Authors: Amano Chikara , Fujiwara Shizuo
Published: July 2006

Tervalent platinum complex ions have been observed by the electron spin resonance method upon γ-irradiation of both bivalent and quadrivalent complexes. From their g-values, the tervalent complex ions can be classified into two types, one axially symmetric and the other rhombic, the former having typical g-values of 2(g⁄⁄) and 2.4(g⊥), and the latter a g1-value slightly lower than the free electron value of 2.0023. It has been shown by means of ligand field theory that both types have 5d7 low spin electron configuration. The hyperfine interaction due to 195Pt is one order of magnitude larger than that in cobalt complexes with 3d7 low spin configuration, indicating that the configuration interaction involving 6s-orbital is more important than that for 3d transition metal complexes involving 4s-orbital, and that 5d electrons penetrate deeply into inner shells, resulting in core polarizarion.
The Effect of NCS− on the Radiation-induced Decoloration of Azo and Anthraquinone Dyes in N2O-saturated Aqueous Solutions
Authors: Suzuki Nobutake , Hotta Hiroshi
Published: July 2006

The radiation-induced decoloration of azo and anthraquinone dyes was studied in N2O-saturated aqueous solutions containing NCS−. In the N2O-saturated solutions, the decoloration yield, G(–Dye), increased markedly upon the addition of NCS−, which is an efficient scavenger of the OH radical—that is, from 1.46 up to 2.10 for Acid Red 265 and from 0.51 up to 1.51 for Acid Blue 40 upon the addition of 1 mM NCS−. In the nitrogen-saturated solutions, however, the G(–Dye) decreased upon the addition of NCS−. It is concluded that the increase in the G(–Dye) upon the addition of NCS− in the N2O-saturated solutions is mainly attributable to the attack of the radical anion (NCS)2− on the ring structure of the dyes. This radical anion is formed through the following path: NCS−+OH→NCS+OH− and NCS+NCS−\ightleftarrows(NCS)2−. At low NCS− concentrations, the G(–Dye) decreased for Acid Red 265 and increased for Acid Blue 40. This may be attributable to the larger reactivity of (NCS)2− on Acid Blue 40 than on Acid Red 265.
Charge-Transfer Absorption of Solid Ion Radical Salts, Application of One-Dimensional Hubbard Model
Authors: Iida Yôichi
Published: July 2006

The electronic spectrum of solid ion radical salt is known to be different from the monomer spectrum of the radical ion and to show an intermolecular charge-transfer band in the low-energy region. In order to understand the character of this charge-transfer absorption, one-dimensional Hubbard model was applied to such solid ion radical salt. The transition energy and the theoretical line shape of the charge-transfer absorption were derived and were compared with those of certain TCNQ, anion radical salts.
Formation of CN(B2Σ+) in the Reaction of Acetonitrile with Metastable Ar(3P2,0) Atoms
Authors: Suzuki Kaoru , Kuchitsu Kozo
Published: July 2006

A flowing-afterglow method was applied to the formation of CN(B2Σ+) from CH3CN by impact of metastable argon atoms, Ar(3P2,0). Emission spectra of CN B2Σ+-X2Σ+ (violet band) were analyzed to estimate the energies distributed to the vibrational and rotational motions of CN(B2Σ+). In comparison with the CN(B2Σ+) produced from HCN under similar experimental conditions, relative populations in excited vibrational states are smaller. The effective rotational temperatures range from 5000±1000 K (v=0–2) to 2000±1500 K (v=5–10). An intensity anomaly caused by the rotational perturbation with A2II is used for estimating the ratio of the formation rates of CN B2Σ+ and A2Π, FB/FA, to be 0.19±0.05.
Ionic Equilibria in Mixed Solvents. XII. Hydrolysis of Cadmium(II) Ion in Dioxane–Water and Methanol–Water Mixtures
Authors: Matsui Haruo , Ohtaki Hitoshi
Published: July 2006

The hydrolytic reactions of cadmium(II) ions were studied at 25 °C in dioxane–water and methanol–water mixtures with varying compositions of the organic solvents, each mixture containing 3 mol dm−3 (Li)ClO4 as an ionic medium. Emf measurements were carried out over the range of the total cadmium(II) concentrations of 0.2 to 0.8 mol dm−3 in all the systems. Two complexes Cd2OH3+ and CdOH+ were found in the dioxane–water mixtures, but the latter complex was not detected in the methanol–water system. The formation constant of the Cd2OH3+ complex was slightly larger in the methanol–water mixtures than in the dioxane–water mixtures at the same mole-fraction concentration of the organic solvents.
Reactions of Aminoalkanols with Some Copper(II) Complexes of the Mixed and Non-mixed Bis(Schiff base) Ligands
Authors: Mohankumar V B , Thaker B T , Kohli Rakesh K , Bhattacharya P K
Published: July 2006

Reactions of aminoalkanols have been carried out with mixed and non-mixed bis(Schiff base) complexes of copper(II). In these reactions one of the ligands combines with the aminoalcohol forming a tridentate ligand, wheras another ligand is removed. From the resulting complexes the tendency to form the Schiff base is found to be in the order 2-hydroxybenzophenone≈2-hydroxy-1-naphthaldehyde>salicylaldehyde>2-hydroxyacetophenone. The complexes formed have been characterized by analytical, spectral, and magnetic studies.
Lead(II) Butanedioate–Pentanedioate Mixed Complexes
Authors: Baghel S C , Choudhary K K , Gaur J N
Published: July 2006

Butanedioate and pentanedioate form 1 : 3 highest complexes separately with lead (II) in aqueous medium, three mixed complexes of these two ligands with the metal ion expected in solution being observed. The formation constants of mixed complexes have been evaluated on the basis of polarographic measurements by the method of Schaap and McMasters. The formation constants of the mixed complexes [Pb(X)(Y)]2−, [Pb(X)(Y)2]4−, and [Pb(X)2(Y)]4− are 3.57, 4.22, and 4.49 respectively in their logarithmic form at 303 K, where X2− and Y2− stand for butanedioate and pentanedioate ion, respectively. The statistically calculated values of logarithm of formation constants are 3.43, 4.43, and 4.49 in the above order. The small differences in the observed and calculated values may be due to electrostatic, steric etc. factors. The relative probability of the existence of these mixed complexes and also simple complexes has been explained.
Isolation of Enammonium Salt and Its Rearrangement to the Corresponding Iminium Salt
Authors: Matsushita Hajime , Tsujino Yasuko , Noguchi Masao , Yoshikawa Sadao
Published: July 2006

Enammonium salt of 2-methyl-1-(β-methylstyryl)piperidine (1) was isolated for the first time and characterized. The enammonium salt, 2-methyl-1-(β-methylstyryl)piperidinium chloride (2), was found to change easily to the corresponding iminium salt, 2-methyl-1-(2-phenylpropylidene)piperidinium chloride (3), at room temperature. The structure of the salts derived from 1-(β-methylstyryl)piperidine (4), 2-methyl-1-(β-methyl-styryl)pyrrolidine (5), 1-(β-methylstyryl)pyrrolidine (6), 1-(2-methyl-1-propenyl)pyrrolidine (7), and 2-methyl-1-(2-methyl-1-propenyl)piperidine (8) were also examined.
Direct Synthesis of Methyl Isobutyl Ketone by Reductive Aldol Condensation. III. Kinetics
Authors: Watanabe Yoshiaki , Okada Masato , Izumi Yusuke , Mizutani Yukio
Published: July 2006

The kinetics of the direct catalytic conversion of acetone and hydrogen into methyl isobutyl ketone (MIBK) were investigated in the liquid phase using palladium–zirconium phosphate as a catalyst. Kinetic studies on the conversion of acetone into mesityl oxide (4-methyl-3-pentene-2-one) and its hydrogenation were separately carried out using the same catalyst. It was found that the direct reaction proceeded via a sequence of processes: mesityl oxide was first formed by condensation of acetone on acid sites of the catalyst and MIBK was then produced by hydrogenation of the mesityl oxide on palladium metal in the catalyst. Moreover, the experimental results were well interpreted by assuming that the condensation of acetone was controlled by a surface reaction between the acetone molecules adsorbed on the catalyst surface and that the rate of hydrogenation of mesityl oxide was determined by a surface reaction between dissociated hydrogen atoms and adsorbed mesityl oxide molecules.
Studies on Mixed Chelates. VII. Mixed Nickel(II) Chelates Containing N,N′- or N,N′-Dialkylethylenediamines and Acetylacetone
Authors: Nguyen Thi Nga , Fukuda Yutaka , Sone Kozo
Published: July 2006

Twelve mixed nickel(II) chelates with N,N′- or N,N-dimethyl (or diethyl)ethylenediamines and acetylacetonate ion (acac) were prepared, and their properties were compared with those of the similar chelates with N,N,N′,N′-tetramethyl(or tetraethyl)ethylenediamine. With the decrease of the number and bulkiness of the N-alkyl groups in the diamine, the tendency of forming 6-coordinated mixed chelates remarkably increases. The chelates of the type [Ni(diamine) (acac)]X, formed when X is B(Ph)4, which are essentially similar to the corresponding chelates with N,N,N′,N′-tetraalkylethylenediamines, but more apt to combine with solvent molecules and to go over into 6-coordinated structures than the latter.
Chemistry of 1,3-Glycol Derivatives. II. Lithium Aluminium Hydride and Meerwein-Ponndorf-Verly Reductions of 6,6-Dimethylspiro[2.5]octane-4,8-dione
Authors: Itoh Osamu , Okita Tsutomu , Umezu Makoto , Inoue Masashi , Ichikawa Katsuhiko
Published: July 2006

Lithium aluminium hydride reduction of 6,6-dimethylspiro[2.5]octane-4,8-dione in tetrahydrofuran gave cis- and trans-6,6-dimethylspiro[2.5]octane-4,8-diols. Almost the same ratio of cis: trans=1:2 was obtained with various substrate-reagent ratios. In the case of Meerwein-Ponndorf-Verly reduction, however, cis-diol was obtained almost exclusively. It is clear that the former reduction gave kinetically-controlled products and that the latter gave thermodynamically-stable products. Unusual results were obtained by changing the hydrolysis conditions for the lithium aluminium hydride reduction products and these are explained assuming that the intermediate aluminium alkoxide is oxidized by acid.
Reactions of a Variety of Diazoalkanes with o-Sulfobenzoic Anhydride
Authors: Oshima Takumi , Nagai Toshikazu
Published: July 2006

It was found that a number of diazoalkanes (I) bearing a relatively small substituent reacted with o-sulfobenzoic anhydride (II) in acetonitrile at an ordinary temperature to give the o-(substituted glycoloyl)benzenesulfonic acid sultones (IV), which correspond formally to the products from the insertion into the C–O bond of II by the carbenes, while diaryldiazomethanes underwent decomposition under the same conditions to produce the corresponding tetraarylethylenes (V) instead of the inserted products (IV). The olefin formation reaction was very fast compared to the sultone formation and was considered to be the result of the acid-catalyzed decomposition caused by the contaminant o-sulfobenzoic acid (III) which was derived from II. The kinetics and the mechanism of these reactions were discussed on the basis of the nature of diazoalkanes.
Fundamental Studies on the Ion-Exchange Separation of Boron Isotopes
Authors: Kakihana Hidetake , Kotaka Masahiro , Satoh Shohei , Nomura Masao , Okamoto Makoto
Published: July 2006

The single-stage separation factors for boron isotopes between an ion-exchange resin and an external solution were determined, using an ion-exchange breakthrough operation. The lighter isotope boron-10 was considerably enriched in the anion-exchange resin phase. The separation factor was very much influenced by the boric acid concentration in the external solution, but not as much influenced by the kind of the anion exchange resin used and operation temperature. The separation factor increased with a decrease in the boric acid concentration of external solution from 1.008 (0.501 mol/l) to 1.016 (0.010 mol/l). The value of the separation factors obtained experimentally were compared with those estimated on the basis of the theory of the two-phase distribution of isotopes.
A Practical Synthesis of Polyhalomethyllithium-Carbonyl Adducts
Authors: Taguchi Hiroaki , Yamamoto Hisashi , Nozaki Hitosi
Published: July 2006

The title adducts are produced upon treatment of a mixture of polyhalomethane and a carbonyl compound with a hindered lithium amide. The kinetically controlled, selective lithiation of the halide enables us to avoid a troublesome procedure involving preformed lithium carbenoid. The halide components examined are dichloromethane, dibromomethane, diiodomethane, chloroform, and bromoform, while the carbonyl ones are ubiquitous ketones and nonanal. A gem-dichloroallyllithium is generated similarly from 3,3-dichloropropene and, furthermore, the procedure is successfully extended to the Darzens-type reaction of α-halo esters.
Carbon-13 NMR Spectra of π-Allyl Palladium Chloride Complexes
Authors: Senda Yasuhisa , Suda Hiroshi , Ishiyama Jun-ichi , Imaizumi Shin , Kasahara Akira , Izumi Taeko , Kato Takao
Published: July 2006

The 13C NMR spectra of thirteen acyclic and cyclohexenyl π-allyl palladium chloride dimers are examined and their chemical shifts are compared with those of the corresponding olefins. The signals for the central carbons of the π-allyl palladium moiety were displaced upfield by 8.0–25.5 ppm and those for the terminal carbons by 34.9–55.9 ppm compared to the corresponding carbons of the corresponding olefins.
Accordionlike Skeletal Motions of CH3NHCONH(CH2)nCH3 (n=1–15)
Authors: Mido Yoshiyuki , Fujita Fumiko , Kitagawa Teizo
Published: July 2006

Solid CH3NHCONH(CH2)nCH3 (n=1–15) gave two intense Raman lines in the 100–500 cm−1 region. The frequency of one of them varied with n, but that of the other was unvarying. The n-dependent frequencies fit the theoretical ν-δ curve of C–C–C deformation of polyethylene and were, therefore, assigned to the accordion modes.
The Channeling of Hot H Atoms in the Radiolysis and Photolysis of Crystalline Alkane
Authors: Miyazaki Tetsuo
Published: July 2006

The possibility of a long migration of hot H atoms through crystalline alkane is discussed in terms of a simple channeling theory. The potential energy surface for an H atom in crystalline neopentane shows that the channeling directions are perpendicular to the [110] and [100] planes. The energy dependence of the channeling of hot H atoms is discussed.
The Coercive Force of γ-Fe2O3 Prepared from γ-FeOOH
Authors: Hamada Shuichi , Kuma Kenshi
Published: July 2006

The γ-Fe2O3 with a high coercive force was prepared by reducing the acicular γ-FeOOH at 300 °C and by then reoxidizing it at 250 °C. A conversion from γ-FeOOH to γ-Fe2O3 at lower temperatures was effective in obtaining acicular particles without pores because of the large mobilities of ions in the crystal.