bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Reaction of Cobalt Hydrocarbonyl with Vinylacetate, Crotonate, Styrene, and Acrylates
Authors: Suga Sohei , Masada Hiromitsu , Suda Haruki , Watanabe Yoshihisa , Takegami Yoshinobu 
Published: July 2006

Abstract
Ethyl vinylacetate and ethyl crotonate reacted with cobalt hydrocarbonyl at 25°C to give three isomeric acylcobalt carbonyls, α- and γ-carbethoxy-butyrylcobalt carbonyls and β-carbethoxy-iso-butyrylcobalt carbonyl. The distribution of these complexes depends greatly on the reaction time (0.5–20 hr). In both cases the β-isomer predominates at shorter reaction times (0.5–1.5 hr), while the γ-isomer predominates at longer reaction times. This shows that isomerization occurs among the complexes and that the equilibrium is very favorable to the γ-isomer. Acrylates and styrene react with cobalt hydrocarbonyl to give two isomeric acylcobalt carbonyls. The isomerization of the acylcobalt complex with a branched structure to that with a straight-chain structure is much promoted by the phenyl and ester groups. The promoting effect of the ester groups is the highest in benzyl, followed by allyl, and ethyl, isopropyl, butyl, and cyclohexyl. Such a promoting effect can reasonably be attributed to the −I effect of these groups.
Reactions of Diazoketones in the Presence of Metal Chelates. II. Reactions with Olefinic Compounds
Authors: Takebayashi Matsuji , Ibata Toshikazu , Kohara Hideki , Ueda Kozaburo 
Published: July 2006

Abstract
The reaction of α-diazoacetophenone with olefinic compounds, such as vinyl acetate, cis- and trans-stilbenes and cyclohexene, has been studied in the presence of bis(acetylacetonato)copper-(II). The reaction gave the corresponding cyclopropane derivatives, the addition products of benzoylcarbene to the double bond of olefinic compounds in good yields, accompanied by cis-and trans-dibenzoylethylenes, dibenzoylethane or dilactone. Addition of carbene was found to be stereospecific in the cases of cis- and trans-stilbenes. A mechanism has been advanced in which a ketocarbene-metal chelate complex is included as an intermediate of the reaction.
The Structure-Stability Relationship of the Metal Ion Complexes of Unsaturated Compounds. V. Stabilities of the Silver-Ion Complexes of Some cis-Stable Olefins
Authors: Okuyama Tadashi , Fueno Takayuki , Furukawa Junji 
Published: July 2006

Abstract
The silver-ion complexation equilibria of a few cis-stable olefins have been investigated in an aqueous phase at 25°C. The trans isomers of β-chlorovinyl ethyl ether and 1,2-dichloroethylene were found to have greater equilibrium constants than the corresponding cis isomers. It was concluded that the relative stabilities of parent olefin isomers play an exclusive role determining their relative complexation abilities.
Polarographic Study of Metal Complexes. IX. Halogeno- and Aquo-bis(dimethylglyoximato)amminecobalt(III) Complexes
Authors: Maki Nobufumi , Ishiuchi Yukio , Sakuraba Shukichi 
Published: July 2006

Abstract
The halogeno- and aquo-bis(dimethylglyoximato)amminecobalt(III) complexes of the trans-[CoIIIX dg2(NH3)]-type have been found to be reduced to the metal through the cobalt(I) state in a 0.5m Na2SO4 aqueous solution at the dropping mercury electrode (DME), where the ligand, X, denotes the ion, Cl−, Br−, or I−, or the molecule, OH2. The aquation of the halogeno complexes is found to take place more rapidly in solution in this order: Cl−&lt;Br−&lt;I−. The diaquobis(dimethyl-glyoximato) cobalt(III) ion, [Co(OH2)2dg2]+, has also been ascertained to undergo a step-by-step reduction to the metal through the cobalt(I) state at the DME.
Nuclear Magnetic Resonance Study of Metal Complexes. I. A Conformational Analysis of d-(l)-Propylenediamine Chelate Rings of Diamagnetic Cobalt(III), Palladium(II) and Platinum(II) Complexes
Authors: Yano Shigenobu , Ito Haruko , Koike Yoshio , Fujita Junnosuke , Saito Kazuo 
Published: July 2006

Abstract
Proton magnetic resonance (PMR) spectra of tetracyano-l-propylenediamine cobalt(III) ion and bis(l-propylenediamine) platinum(II) and palladium(II) ion have been measured in deuterated water and analyzed according to Castellano and Waugh’s exact analysis. The values of coupling constants clearly indicate that the l-propylenediamine chelate rings in these diamagnetic complexes have fixed λ-gauche form in aqueous solutions at room temperature.
Tautomerism in 3-Substituted-2,4-pentanediones and Their Copper Chelates
Authors: Tanaka Minoru , Shono Toshiyuki , Shinra Koichiro 
Published: July 2006

Abstract
Seventeen 3-substituted-2,4-pentanediones were synthesized. The effect of substituents in the position 3 on the tautomeric equilibria, i.e., keto-, cis-enol- and trans-enol-forms, has been investigated by nuclear magnetic resonance spectroscopy. It has been found that the percentage of each tautomer depends upon the electronic and steric effects of the substituents. The relative intensity of intramolecular hydrogen bonds in these compounds was evaluated from both the NMR and IR data. It has been found from the half-wave potential data of polarographic reduction and the Cu–O stretching frequencies of 16 copper chelates of 3-substituted-2,4-pentanediones that the relative stability of the chelate decreases with an increase in the electron-withdrawing effect of the substituents.
Chemical and Spectral Study of 6- and 7-Nitro-2-Methyl, 2-Benzyl, 2-Styryl and 2-(1-Phenylstyryl)-3H-4-Ketoquinazolines and Their 3-Me and 3-Ph Derivatives
Authors: Thakkar R K , Patel S R 
Published: July 2006

Abstract
6- and 7-Nitro-2-benzyl-3H-4-ketoquinazolines and their 3-Me and 3-Ph derivatives were prepared by condensing the 6-nitro (III) and 7-nitro (XII) derivatives of -4H-3,1-benzoxazin-4-one with ammonia, methylamine and aniline, respectively. The compounds III and XII were formed on refluxing 5- and 4-nitro-N-phenylacetylanthranilic acids with acetic anhydride. 6- and 7-Nitro-2-benzyl-3H-4-ketoquinazolines (IV and XIII) were also prepared by condensing 5- and 4-nitro-N-phenylacetylanthranilic acids with formamide, respectively, in very low yields. The compounds IV and XIII yielded the corresponding 2-benzoyl derivatives on oxidation and the corresponding 2-(1-phenylstyryl) derivatives on reaction with benzaldehyde. 6- and 7-Nitro-2-styryl and 2-(1-phenylstyryl)-3H-4-ketoquinazolines were not oxidized by alkaline permanganate. UV spectra of these compounds have been studied.
Crystalline Terpolymer of Formaldehyde, Carbon Dioxide, and N-Phenylethylenimine
Authors: Kagiya Tsutomu , Narita K\={o}z\={o} , Kondo Masatsune 
Published: July 2006

Abstract
Formaldehyde, carbon dioxide, and N-phenylethylenimine were allowed to terpolymerize by means of dimethyl ether acetate to give a crystalline solid terpolymer, melting at 178–265°C, with the composition of: CH2O: 70–95, CO2: 0.5–5, C8H9N: 5–25 mol%. The content of N-phenylethylenimine in the terpolymer thus obtained increased with the content of the imine in the feed, and that of carbon dioxide in the terpolymer, with the content of the imine in the feed, the lowering of the polymerization temperature, and the polymerization time. The infrared spectrum of the terpolymer showed the characteristic peaks of –(–CH2OCH2O–)–, (Remark: Graphics omitted.) and (Remark: Graphics omitted.). The mechanism of the terpolymerization was proposed on the basis of these results.
Formulas for One- and Two-center Moment Integrals between Slater Type s,p-Orbitals with Integer Effective Principal Quantum Numbers of 1 to 5
Authors: Suzuki Masaru , Nihei Yoshimasa , Kamada Hitoshi 
Published: July 2006

Abstract
Expansion formulas are presented for one- and two-center moment integrals between Slater type s,p-orbitals with integer effective principal quantum numbers of 1 to 5, together with the procedure. These formulas are useful in the calculation of a dipole moment and a transition moment from a charge distribution calculated by LCAO-MO method. A FORTRAN subprogram containing most of these formulas, which are important in practice, occupies about 7.7K of the core memory of a computer, HITAC 5020.
Characterization and Some Reactions of Peroxy-trans-crotonic Acid
Authors: Yoshizawa Ryo , Inukai Takashi 
Published: July 2006

Abstract
Peroxy-trans-crotonic acid was prepared from dicrotonyl peroxide by alkaline cleavage and isolated for the first time in a crystalline state, mp 41–42°C. It was characterized by NMR and IR spectra, and its stability briefly tested. Reaction with dimethyl sulfide gave a quantitative yield of crotonic acid. Its pKa in water at 25°C was 8.2. Second order rate constants of reaction with crotonaldehyde in benzene (Table 4) were measured: Ea, 13.3 kcal/mol; log A(l/mol sec), 5.3; ΔS\eweq, −36 eu/mol. Detection of a possible intermediate, a peracid-aldehyde complex X, was attempted by means of NMR but evidence for it was not obtained.
One-Electron Reduction of Carbonium Ions. II. Reduction of the Tropylium Ion and the Triphenylmethyl Cation with Metallic Powders and Metallic Ions
Authors: Okamoto Kunio , Komatsu Kôichi , Shingu Haruo 
Published: July 2006

Abstract
The reaction of tropylium fluoroborate in an aqueous solution has been carried out at room temperature with powders of various metals (Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, Cu, Hg, and Ag) under heterogeneous conditions and with several metallic ions (Cr(II), Ti(III), Sn(II), Cu(I), Fe(II), Fe(III), Hg(I), Hg(II), and Ag(I)) in a homogeneous solution. All these reagents, except Ag, Fe(III), Hg(I), Hg(II), and Ag(I), reduce with ease the tropylium ion to give the tropyl radical, which then rapidly couples to bitropyl; their reducing powers, estimated by comparing the yields of bitropyl under the same reaction conditions, correlate with their oxidation electrode potentials and oxidation-reduction potentials. The ferric ion, the mercurous ion, the mercuric ion, and the silver ion afforded no bitropyl, but only an oxidation product of the tropylium ion, i.e., benzaldehyde. Silver powder gives neither a reduction nor an oxidation product under these reaction conditions. The reduction has also been carried out in an acetonitrile solution, and the reducibility of tropylium fluoroborate with powders of Zn, Fe, Ni, Sb, Cu, and Ag has been compared with that of triphenylmethyl fluoroborate under heterogeneous conditions. Both the tropylium ion and the triphenylmethyl cation are smoothly reduced by Zn, Fe, Ni, Sb, and Cu in this solvent. The tropylium ion, however, is not reduced by silver powder, while the triphenylmethyl cation is reduced to the triphenylmethyl radical. This greater reducibility of the triphenylmethyl cation is consistent with what could be anticipated from the data of half-wave potentials, ionization potentials, and H.M.O. calculation reported with respect to these two carbonium ions.
Intermolecular Hydrogen Bond Involving a π Base as the Proton Acceptor. IX. Hydrogen Bonding of Phenol to Monoolefins
Authors: Yoshida Zen-ichi , Ishibe Nobuyuki 
Published: July 2006

Abstract
The π hydrogen bonding between phenol and monoolefins has been studied by examining the OH stretching vibration spectra of phenol in the presence of monoolefins. From comparison of the hydrogen bond shifts, it has been shown that the basicity of the aliphatic olefins toward phenol increases with the increasing alkylsubstitution on the double bond carbon. The endo-cyclic olefins are more basic than RCH=CH2 and RCH=CHR′ where R and R′ represent alkyl groups. The equilibrium constants for complex formation with olefins were smaller than those with aromatic hydrocarbons. The steric effects on the hydrogen bond complex with aliphatic and endocyclic olefins have been discussed.
β-Ferrocenyl-α,β-unsaturated Ketones. I. Condensation Reactions of Formylferrocene with Ketones
Authors: Kono Hiromichi , Shiga Mikio , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
The condensation reaction of formylferrocene with simple aliphatic and alicyclic ketones, as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone, in the presence of piperidine as a condensing agent afforded seven kinds of β-ferrocenyl-α,β-unsaturated ketones. The geometric configurations of the unsaturated ketones were discussed on the basis of their NMR spectra, and the influences of the ferrocenyl group on the π-π* transition bands in their UV spectra were also discussed.
Reactions of Alkyltropylium Ions with a Base
Authors: Nozoe Tetsuo , Takahashi Kazuko , Yamamoto Hiroshi 
Published: July 2006

Abstract
On the reaction with a base (e.g., aqueous sodium hydroxide), isopropyl- and methyl-tropylium ions afforded cycloheptatrienyl polymers with an alkylene bridge, such as IIIa and IIIb, while the t-butyltropylium ion gave a mixture of 3- and 4-t-butyltropone, which was then transformed to 4-and 5-t-butyltropolone (VIIIa and IX). The bromination of VIIIa with 3 mol of bromine in methanol gave 3,7-dibromo-4-t-butyl-2-methoxy-2,3-dihydrotropolone (XIIa). On the heating of the adduct (XIIa) at 130°C, 7-bromo-4-t-butyltropolone (XIa) was formed.
The Efficiencies of Hydrocarbons and Hydrogen in Quenching Triplet Cadmium Atoms
Authors: Tsunashima Shigeru , Satoh Shin , Sato Shin 
Published: July 2006

Abstract
The relative efficiencies of sixteen hydrocarbons and of hydrogen in quenching triplet cadmium atoms have been measured at 270±1°C by the competitive quenching method, using the cadmiumphotosensitized cis-trans isomerization of cis-2-butene as a detector reaction. The quenching efficiencies of all the olefins studied and of acetylene were almost the same. The efficiencies of saturated hydrocarbons were, however, very low compared with those of unsaturated ones. Hydrogen was as efficient as unsaturated hydrocarbons.
Effects of the Nitrone Group in NMR Spectra of α,N-Diphenylnitrones
Authors: Koyano Kinko , Suzuki Hiroshi 
Published: July 2006

Abstract
The NMR and UV spectra of α,N-diphenylnitrone and its derivatives which have a substituent at the para position of the α-phenyl group and some of which have in addition a methyl substituent at the ortho position of the α-phenyl group were measured. Examination led to the following conclusions. The NMR signal of the ortho protons of the α-phenyl group appears at a very low field. This is mainly attributed to the direct effect of the negatively charged oxygen atom of the nitrone group. Increase in the electron-donating power of the para substituent enhances this effect.
Synthetic Reactions by Complex Catalysts. XIV. Reaction of Isocyanide with Amine Catalyzed by Group IB and IIB Metal Compounds
Authors: Saegusa Takeo , Ito Yoshihiko , Kobayashi Shiro , Hirota Kiwami , Yoshioka Hiroshi 
Published: July 2006

Abstract
Group IB and IIB metal compounds catalyze the reaction of isocyanides (1) with amines (2) producing formamidines (3). In the reaction of cyclohexyl isocyanide with piperidine, the accelerating effect of catalyst was in the order AgCl&gt;CuCl&gt;&gt;ZnCl2, Cd(OAc)2, HAuCl4·4H2O. The AgCl catalyzed reaction proceeded almost quantitatively in 2.5 hr at 17°C. The reaction of aliphatic isocyanide with aromatic amine, e.g., N-methylaniline, required higher reaction temperatures (160°C) even in the presence of catalyst, in which the order of catalytic activity was HAuCl4·4H2O&gt;ZnCl2&gt;AgCl&gt;&gt;CuCl. A ternary complex of (CuCl)2 (cyclohexyl isocyanide)2 (piperidine) was isolated, which was unstable and decomposed gradually at room temperature to give N-cyclohexyl-N,N′-pentamethylene formamidine. A mechanism through a mixed ligand complex has been proposed, in which both isocyanide and amine are coordinated with the same metal ion and the reaction takes place in the sphere of complex ligand.
An X-Ray Determination of the Structure of Chamaecynenol
Authors: Shimanouchi Hirotaka , Sasada Yoshio 
Published: July 2006

Abstract
Crystals of chamaecynenol 4-bromo-3-nitrobenzoate, C21H22O4NBr, are monoclinic, with two molecules in a unit cell of the dimensions, a=10.47, b=14.08, c=6.75Å, and β=101.8° and with the space group of P21. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually with a standard scale. The structure was determined by the heavy atom method. The positional and thermal parameters were refined by the least-squares method. The final R factor for the observed reflections is 0.090. The absolute configuration was also determined using anomalous dispersion effect of the bromine atom. It was thus established that chamaecynenol is 7β-ethynyl-4β-hydroxymethyl-10β-methyl-Δ1-cis-octaline in the steroid conformation.
An ESR Study of Photochemical Intermediates from Rigid Organic Solvents Containing Benzene
Authors: Tanei Tadayoshi , Hatano Hiroyuki 
Published: July 2006

Abstract
The present work was undertaken in order to examine a photochemical intermediate from benzene using rigid organic matrices: EPA (a mixture of E: diethyl ether, P: isopentane, and A: ethyl alcohol, 5:5:2, v/v), diethyl ether, and isopentane. The UV irradiation of EPA, diethyl ether, and ethyl alcohol at 77°K, in wavelength regions from approximately 2200Å to 2600Å, gave ESR spectra which can be ascribed to the ethyl and/or the ethanol radical, even when a solute was not added. On the contrary, the UV irradiation of isopentane under similar conditions did not show any ESR spectrum. However, the UV irradiation of isopentane containing benzene in concentration regions from 10−1 to 10−2 m gave two kinds of ESR spectra, ascribed to phenyl and tert-pentyl radicals. This reaction may be interpreted as a sensitized photodecomposition brought about by an excitation and/or a photolytic degradation of benzene.
Infrared Absorption Spectra of Urea-formaldehyde Initial Condensation Products. II. Dimethylurea
Authors: Mido Yoshiyuki , Murata Hiromu 
Published: July 2006

Abstract
The infrared absorption spectra of symmetric and asymmetric dimethylurea have been observed in the 4000—400 cm−1 region. In order to investigate the amide characteristic bands, the spectra of CH3NHCONHCH3 and CH3NDCONDCH3 have also been measured in the solid and liquid states, and in solutions. The in-plane normal vibrations of these molecules have been calculated. As a result of our measurements and calculations, it has been found that: (1) The contribution of the polar resonance structure of asymmetric dimethylurea is small compared with that of symmetric dimethylurea, and molecular geometry contributes to the formation of hydrogen bonding. (2) From the position of the amide bands, the molecular configuration of symmetric dimethylurea is the “trans” form as well as that of methylurea. (3) The results of normal coordinate analysis show a good agreement with that observed within an average deviation of 2.6%.
Effects of Solvent on the Copolymerization of Ethylene with Tetrafluoroethylene by Cobalt-60 Gamma Radiation
Authors: Hagiwara Miyuki , Miura Takeshi , Kagiya Tsutomu 
Published: July 2006

Abstract
The cobalt-60, γ-radiation induced copolymerization of ethylene with tetrafluoroethylene was carried out in the gas phase and in the liquid phase by using five solvents (liquefied carbon dioxide, carbon tetrachloride, ethylchloride, chloropentafluoroethane, and 1,2-dichloro-tetrafluoroethane) at a dose rate of 25000 rad/hr under a pressure of 300 kg/cm2 at 30°C. A lower rate of the copolymerization and a copolymer of a lower molecular weight were obtained in liquid carbon dioxide and carbon tetrachloride than in the gas phase without a solvent. In ethyl chloride, the rate increased slightly, but the molecular weight decreased. On the other hand, both the rate and the molecular weight increased markedly in the fluorocarbon solvents. As a result of a detailed investigation of the copolymerization in 1,2-dichloro-tetrafluoroethane, a linear increase in the copolymerization rate and the copolymer molecular weight with the amount of solvent was noted, and there was no noticiable influence of the solvent on the copolymer composition. A kinetical discussion indicated that the addition reaction of tetrafluoroethylene to radicals produced by the influence of primary radiation on the reaction mixture is an important step in initiating the copolymerization. Also, the propagation reaction seemes to be strongly promoted by the fluorocarbon solvents.
The Low Temperature n–π* Absorption Spectra of the Cyclohexane-1,4-dione Crystal
Authors: Ozeki Kayoko , Tanaka Jiro 
Published: July 2006

Abstract
Cyclohexane-1,4-dione is an aliphatic ketone with two carbonyl groups. The absorption due to the n–π* transition of the carbonyl group extends from the 30000 cm−1 to the 42000 cm−1region. The transition is symmetrically forbidden and is assigned to the A1-A2 transition in the C2v system. The spectra in the crystal and in a solution of EPA at 77°K show only prominent carbonyl stretching vibrations. The polarized single crystal absorption spectra at 4.2°K are composed of many sharp lines; the vibrational structures are analyzed in detail. The 0–0 transition is observed at 31408 cm−1; the distinct basic frequencies of the excited state are 1096, 790, 557, 375, 247, and 122 cm−1, while the lattice vibrations are 61, 32, and 22 cm−1. The transition is explained by the vibronic coupling mechanism, assuming the C2v symmetry for the carbonyl group. Two different types of progressions are noticed; one is induced by the out-of-plane b2-type vibration, while the other is allowed by the a2-type vibration. The dichroic properties of the crystal spectra allowed the assignment of the vibrational modes. These vibrations are compared with the infrared and Raman spectral data.
A Solvent-extraction and Spectrophotometric Study of Copper(II) Complexes in Organic Solvents Containing Acetylacetone and Thenoyltrifluoroacetone
Authors: Hasegawa Yuko 
Published: July 2006

Abstract
The complex-formation equilibria of copper(II) in chloroform, benzene, or methyl isobutyl ketone (MIBK) containing both acetylacetone (AA) and thenoyltrifluoroacetone (TTA) have been determined by means of a liquid-liquid distribution method and a spectrophotometric method. The extraction constants or the extinction coefficients of the pure complexes were first determined in solutions containing only one of the liquids, and then these constants for the mixed complex and the equilibrium constants among the three complexes in these solvents were determined by the analysis of the results obtained from the experiments in mixed-ligand solutions. From these data, the following conclusions were reached. The constants experimentally obtained are almost identical with those statistically expected. The absorption spectrum of the mixed complex isolated from the absorption of the mixed-ligand system by the statistical analysis is more similar to that of the TTA complex than to that of the AA complex. The results obtained by these two methods are somewhat different from each other.
Group Theoretical Treatment of Crystal Vibrations; Application to Orthorhombic Polyethylene
Authors: Kitagawa Teizo , Miyazawa Tatsuo 
Published: July 2006

Abstract
Irreducible representations of k groups of the space group Pnam were derived with Slater’s method. Degeneracies of crystal vibrations due to space symmetry and time reversal symmetry were treated on the basis of Maradudin’s theory. With irreducible representations of k groups, symmetry coordinates of the carbon atoms of orthorhombic polyethylene were constructed from translational-symmetry coordinates with nonintegral index vectors. A general matrix method was worked out for treating crystal vibrations of any phase-difference vector. Useful methods were derived for treating molecular crystals and chain polymer crystals and for approximate treatment of low frequency lattice vibrations.