bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Infrared Spectra of Metallooctaethylporphyrins
Authors: Ogoshi Hisanobu , Masai Naruhito , Yoshida Zen-ichi , Takemoto James , Nakamoto Kazuo 
Published: July 2006

Abstract
The infrared spectra of the Mg(II), Co(II), Cu(II), Zn(II), Pd(II), Ni(II), and Ge(IV)Cl2 complexes of octaethylporphyrins have been studied over the range 4000–100 cm−1. Metal sensitive bands have been observed at about 980, 920, 340, 230, and 130 cm−1.
Studies of Compounds Related to Azines. VII. The Pyrorlysis of 2-Acetylthiophene- and 2-Acetylfuranketazine
Authors: Tsuge Otohiko , Watanabe Haruyuki , Hokama Kozo 
Published: July 2006

Abstract
As part of a study attempting to elucidate the relation between the chemical structure of an azine and its pyrolysate, the pyrolyses of 2-acetylthiophene- (I) and 2-acetylfuranketazine (II) have been investigated. The pyrolysis of I at 270°C afforded principally nitrogen, ammonia, and 7-methy 1-5-(2-thienyl)-thieno[2,3-c]pyridine (III), plus lesser quantities of thiophenecarbonitrile and 2-acetylthiophene. The reductive desulfurization of III, followed by oxidation, afforded pyridine 2,4,6-tricarboxylic acid via 5-n-butyl-7-methyl-thieno[2,3-c]pyridine and 2-n-butyl-4-ethyl-6-methylpyridine. On the other hand, II was pyrolyzed to give nitrogen, ammonia, and tars as the major products, together with furan, furancarbonitrile, 2-acetylfuran, 5-(2-furyl)-7-methyl-furo[2,3-c]pyridine, and 2,4,6-tri(2-furyl)pyridine.
Stoichiometric Carbonylation of Aryl Halide with Nickel Tetracarbonyl in the Presence of Potassium Acetate
Authors: Nakayama Mikitake , Mizoroki Tsutomu 
Published: July 2006

Abstract
In the stoichiometric reaction of aryl halide with Ni(CO)4 in methanol to form the corresponding ester, it has been found that the carbonylation is effectively promoted by adding potassium acetate to the starting materials, and that four moles of the ester are obtained from one mole of Ni(CO)4 without any appreciable side reactions. From the inhibition by gaseous carbon monoxide and the IR measurements during the carbonylation, it has been concluded that nickel tricarbonyl, Ni(CO)3, is the initiator of the carbonylation and that its regeneration is the rate-determining step. The present results provide a basis on which the course of the carbonylation of aryl halide with carbon monoxide catalyzed by Ni(CO)4 under high temperatures and pressures may be reasonable explained.
Polarography of Halides in Dimethylformamide. VI. The Formation of the Benzhydryl Radical from Benzhydryl Bromide and Its Subsequent Reduction at the Dropping Mercury Electrode
Authors: Matsui Yoshihisa , Soga Takashi , Date Yoshio 
Published: July 2006

Abstract
The polarographic behavior of benzhydryl bromide at the dropping mercury electrode was investigated in dimethylformamide at 25degC. It gives three waves, with half-wave potentials at about +0.19, −0.15, and −1.00 V vs. SCE. The first wave is anodic, while the others are cathodic. It was concluded that benzhydryl bromide, prior to being electrolytically reduced, rapidly reacts with the mercury of the cathode according to the following equation:
3(C6H5)2CHBr+Hg→2(C6H5)2CH·+(C6H5)2CH++HgBr3−
The first wave given by the bromide was ascribed to the oxidation of HgBr3− to HgBr2; the second, to the reduction of HgBr3− to Hg and Br−, and the third, to the reduction of (C6H5)2CH· to (C6H5)2CH−. The cation, (C6H5)2CH+, was found to give no wave. Such behavior of benzhydryl bromide was discussed in comparison with that of the corresponding chloride, which gives a single wave with a usual two-electron transfer.
The Mechanism of the Reaction of Quinolines with Organolithium Compounds
Authors: Otsuji Yoshio , Yutani Kiyihiko , Imota Eigi 
Published: July 2006

Abstract
The treatment of lepidine (IV) with phenyllithium in ether afforded 2-phenyl-4-methylquinoline (V) along with small amounts of 2-phenylquinoline (VI) and 2-methyl-4-phenylquinoline (VII). The similar treatment of IV with phenyllithium and then with ethyl chloroformate gave 1-ethoxycarbonyl-4-methyl-4-phenyl-1,4-dihydroquinoline (VIIIa). The alkaline hydrolysis of VIIIa produced a mixture of V, VI, and VII. Similar experiments were carried out on the reactions between IV and n-butyllithium and between quinoline and phenyllithium. On the basis of these results and other observations, a new mechanism involving an addition-rearrangement-elimination was proposed for the reaction of quinolines with organolithium compounds.
The Cationic Polymerization of Methallyl Vinyl Ether
Authors: Yuki Heimei , Hatada Koichi , Emura Tomoyuki , Nagata Kazuhiko 
Published: July 2006

Abstract
The polymerization of methallyl vinyl ether was carried out in toluene by means of BF3·OEt2. The reaction proceeded through the vinyl double bond, giving a polymer containing one methallyl double bond per monomeric unit. The polymer obtained below −78°C was a white powder and had an isotactic configuration. The molecular weight of the polymer decreased with an increase in the polymerization temperature, and the polymer obtained at 0°C was a viscous liquid. In n-heptane, the yields of the polymer decreased and a part of the polymer obtained was insoluble in usual organic solvents, probably because of the cross-linking which occurred during the polymerization reaction. In n-heptane-toluene mixtures, the yields were much higher than those in toluene or n-heptane alone. The NMR spectra of the polymer were measured in CCl4, benzene, pyridine, and quinoline at various temperatures in order to investigate the polymer-solvent interaction; the π-complex formation between the monomeric unit of the polymer and the aromatic solvent molecule was suggested.
4-Acetylierung der 5-Hydroxy-indol-Derivate
Authors: Suehiro Tadashi , Niitsu Machiko 
Published: July 2006

Abstract
5-Hydroxy-4-acetyl-2-äthoxycarbonyl-indol und 5-Hydroxy-2-methyl-4-acetyl-indol wurden durch die Friedel-Crafts-Acetylierung oder durch die Fries-Umlagerung in Gegenwart von Lewis-Säure bzw. unter Belichtung hergestellt. Die Acetylierung wird stark von dem sterischen Faktor des 3-Subtituenten beeinflusst und bei 5-Hydroxy-2-methyl-3-äthoxycarbonyl-indol läuft die 6-Acetylierung ab. Wenn kein 3-Substituent vorhanden ist, wird es eher an der 4-Stellung als an der 6-Stellung acyliert. Der Strukturbeweis wurde aus den NMR-Spektren geführt. 5-Hydroxy-4-acetyl-2-äthoxycarbonyl-indol lässt sich in Dimethylformamid durch Natriumhydrid und Alkylhalogenid an den O- und N-Stellungen alkylieren.
The Chemisorption of Nitric Oxide and Nitrogen on Rhenium
Authors: Tamura Teijiro 
Published: July 2006

Abstract
The chemisorption of nitric oxide and nitrogen on a polycrystalline rhenium filament was studied using flash-desorption mass spectroscopy. For the chemisorption of nitric oxide, the initial sticking probability was found to be close to unity, with a saturation coverage of 5.2×1014 molecules/cm2 at room temperature. Nitric oxide adsorbs nondissociatively, and dissociation occurs at an elevated temperature. The rate of the desorption of nitrogen from the nitric oxide layer is roughly proportional to θ2. The majority of the oxygen in the nitric oxide layer was presumed to be liberated as rhenium oxide. The nitrogen adsorption was investigated in order to compare it with the nitric oxide adsorption. The saturation coverage and the initial sticking probability were 1.08×1014 molecules/cm2 and 0.003 respectively.
Inter and Intramolecular Charge and Excitation Transfer Observed in Irradiated Polyvinyl Chloride Particles with Surface-coated Additives
Authors: Ueda Hisashi , Yashiro Dairokuro 
Published: July 2006

Abstract
Particles of polyvinyl chloride were coated with small amounts of various aromatic compounds from benzene solutions and were then irradiated in a vaccum. The ESR spectra of the specimen thus obtained were recorded. Though the amount of the coated additives, in the ratio of 1 molecule for 100 monomer units of PVC, was small, strong effects on the ESR spectra were observed. The additives coated on the surface affect the ESR spectra in two ways. They cause a decrease in the total ESR absorption intensity; this was observed with all the additives studied. They also often transform the ESR spectrum; this was observed with several additive compounds, such as p-benzoquinone, tetramethylphenylenediamine-2·HCl, chrysene, hydroquinone, nitrosonaphthol, perylene, and diphenylpicrylhydrazine. Only the conduction of the excitations, holes and electrons formed in the bulk particles, to the surface of the particle can explain these results. On the surface of the particle, the excitation or the electric charge is transferred to the additive by means of an intermolecular interaction with it. The possibilities for the mechanism of the conduction of the excitation and the electric charges, and the ionization processes are discussed.
The Electrodeposition of Aluminum from a Solution of Aluminum Bromide in N,N-Dimethyl Aniline
Authors: Hisano Takeo , Terazawa Toshio , Takeuchi Ichiro , Inohara Shinzo , Ikeda Hiroshi 
Published: July 2006

Abstract
This paper will describe that metallic aluminum was deposited electrolytically from a solution of aluminum bromide in dimethyl aniline with a current efficiency of 95% or more under optimum conditions. The superposition of a sinusoidal alternating current (AC) on the electrolysis direct current (DC) affected the properties of coatings and the throwing power of solutions to a great extent. A smooth, white-bright, ductile, and adherent coating was obtained under such appropriate conditions as that the frequency of AC was 60 Hz, the AC to DC ratio of 2 to 3. Aluminum dissolved anodically, and it was deposited at the cathode. The freezing temperature-composition diagram indicated the occurrence of two stoichiometric molecular complexes, AlBr3·C6H5N(CH3)2 and AlBr3·2C6H5N(CH3)2, and the former was isolated.
Electronic Structure of Lone Pairs. II. Disulfides and Acyl Thiol
Authors: Yamabe Hiroko , Kato Hiroshi , Yonezawa Teijiro 
Published: July 2006

Abstract
The electronic structure and the electronic transition of three cyclic disulfides, (CH2)3S2, (CH2)4S2, and (CH3)2S2, are calculated by the semi-empirical ASMO SCF method in order to study the interaction of the neighbouring lone pairs of the S–S bond in connection with the ability of reductive scission. It is concluded that the absorption at 2500–3000 Å is the transition of n–σ* and that the variation in the maximum for the various cyclic disulfides and the chain disulfide are induced by the change in the dihedral angle that a molecule can take. The electronic structure and the reactivity of (CH3)2S2, CH3SSH, and CH3SCOCH3 are then discussed on the basis of an extended Hückel calculation. It is suggested that there is the possibility of an interaction between two molecules, R2S2, through the S–S bond of each molecule, in the HO of one molecule and in the LV of another.
The Optical Activity of Bis-1,1′-spiroindanes. The Direct Calculation of Optical Rotational Strengths
Authors: Hagishita Sanji , Kuriyama Kaoru 
Published: July 2006

Abstract
A calculation based on Longuet-Higgins and Murrell’s method using the MO’s of aniline and phenol obtained by the SCF-MO-CI calculation is carried out for the π-electron structures of (−)-6,6′-diamino-(I) and (−)-6,6′-dihydroxy-bis-1,1′-spiroindane (II). These wave functions are then used to calculate the rotation strengths of these compounds. The circular dichroism curves calculated from the results, assuming a Gaussian curve, are compared with the observed spectra; a quantitative agreement with the experimental value is found. The nature of the transitions and the origin of the optical activity are also discussed.
The Cation Radical Salts of Phenothiazine and Related Compounds
Authors: Iida Yôichi 
Published: July 2006

Abstract
The cation radical salts of phenothiazine bromide, phenothiazine bisulfate monohydrate, and phenothiazine picrate were prepared. The absorption spectra in a dilute hydrochloric acid solution and the solid-state spectra of the salts were examined. The solid-state spectra showed a strong charge-transfer band and blue-shifts of the high-energy bands, unlike the absorption spectra in solution. The magnetic susceptibilities of these salts were measured at room temperature. They were found to be diamagnetic, with values almost corresponding to those of the diamagnetic contribution of the salts, except for that of the picrate. These spectroscopic and magnetic properties were discussed on the basis of the charge-transfer interaction between the phenothiazine cation radicals. The properties of the usual phenothiazine-picric acid charge-transfer complex and the holoquinoid phenothiazine perchlorate were investigated in association with those of the cation radical salts.
Studies of the Formation Mechanism of Sodium Tripolyphosphate from Orthophosphates by the Use of Radioisotopes
Authors: Iida Takaya , Takai Nobuharu , Yamabe Takeo 
Published: July 2006

Abstract
The reaction process of an equimolar mixture of mono- and disodium orthophosphates was examined to serve as a reference for the considerations of the mechanism of the formation of sodium tripolyphosphate. Differential thermoanalysis, thermogravimetric analysis, X-ray diffraction analysis and thin-layer chromatographic analysis were done. Particularly, the reaction mechanisms (the formation of liquid Na3HP2O7, etc.) were also examined by the use of the “32P” radioisotope. The reaction process is as follows:
(Remark: Graphics omitted.)
A feedback phenomenon of Na2H2P2O7 was observed.
Derivatographic Studies on Transition Metal Complexes. VI. Thermal, cis, trans-to-cis, cis Exchange-Isomerization of [CoCl2(NH3)2en]SCN·H2O in Solid Phase
Authors: Tsuchiya Ryokichi , Suzuki Masatatsu , Kyuno Eishin 
Published: July 2006

Abstract
The exchange-isomerization of the complex, cis(dichloro), trans(diammine)-[CoCl2(NH3)2en]SCN·H2O to cis(chloro isothiocyanato), cis(diammine)-[CoCl(NCS)(NH3)2en]Cl, was investigated by means of both derivatographic and isothermal methods. The reaction took place immediately after the liberation of crystalline water. The thermochemical functions were obtained to be ΔH=(5.5±1.0) kcal/mol and E≠=(22.8±2.0) kcal/mol for the dehydration, while those for the exchange-isomerization were ΔH=(4.8±1.0) kcal/mol and E≠=(62.3±3.0) kcal/mol, respectively. As a probable reaction mechanism for the exchange-isomerization, a certain seven coordinated intermediate in the reaction pathway was introduced.
The Chemical Structures of Glasses of the NaPO3-Sb2O3-Na2O System
Authors: Watanabe Makoto , Tanabe Kazuo , Takahara Tomoyoshi , Yamada Tamotsu 
Published: July 2006

Abstract
Glassy and crystalline substances of the NaPO3-Sb2O3-Na2O system with P/Sb ratios in the range from 1.0 to 300 were prepared by heating NaPO3Sb2O3, and Na2CO3 at 1000°C and by then quenching the melts of the mixtures. Samples with P/Sb ratios smaller than 5.0 were obtained as crystalline substances containing amorphous substances. The chemical compositions of these crystalline substances were estimated from the data obtained by X-ray diffractometry and paper chromatography. Samples with P/Sb ratios larger than 7.0 were obtained as glassy substances. Condensed phosphates were separated by paper-chromatographic analysis, and the average degree of the polymerization of the phosphates was measured by the pH-titration method. It has been found that the crystalline substances in the samples with P/Sb ratios in the range from 1.0 to 5.0 were Sb2O5, NaSbO3, and an unknown crystalline substance. Assuming that the glasses have the P-O-P, P-O−, P-O-Sb, and Sb-O− linkages, a theoretical treatment of the degree of polymerization of condensed phosphates has been made and compared with the experimental data. It has been concluded that the glasses with P/Sb ratios larger than 7.0 have P-O-P, P-O−, and P-O-Sb linkages.
Structure and Intramolecular Motions in Triethylenediamine as Studied by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo 
Published: July 2006

Abstract
The structure and intramolecular motions in triethylenediamine have been investigated by gas electron diffraction with a parallel study of bicyclo[2.2.2]octane in our previous paper. The structural parameters determined by a least-squares analysis on molecular intensities, with estimated limits of error, are as follows: rg(C–N)=1.472±0.007 Å, rg(C–C)=1.562±0.009 Å, ∠C–C–N=110.2±0.4°, ∠C–N–C=108.7±0.4°, rg(C–H)=1.110±0.012 Å and ∠H–C–H=111.5±5.6°. The gas-phase structure is in good correspondence with that in the crystal phase determined by Weiss et al. by X-ray diffraction. The potential function with regard to the twisting motion around the C3 symmetry axis is shown to have a broad minimum around the D3h conformation, being quite analogous to that for bicyclo[2.2.2]octane; in terms of the torsional angle φ about the C–C axis, it probably has a small hump of the order of 100 cal/mol at φ=0° and a double minimum around φ=10°. The above study was made with a new nozzle assembly, by which the sample can be heated to about 200°C. The detail of the design and operation is described.
The Synthesis of Nitro, Amino, and Acetamino Derivatives of 2,3-Dimethylbenzofuran
Authors: Kawase Yoshiyuki , Takata Setsuko , Hikishima Etsuko 
Published: July 2006

Abstract
Another route to the synthesis of nitro, amino, and acetamino derivatives of 2,3-dimethylbenzofuran was explored. The cyclo-dehydration of 3-(m- and p-nitrophenoxy)butanones by means of polyphosphoric acid or sulfuric acid afforded 2,3-dimethyl-4- and -5-nitrobenzofurans, which were then converted by reduction to the corresponding 4- and 5-aminobenzofurans. The 4-, 5-, 6-, and 7-aminobenzofurans were prepared by the Hofmann reaction of the corresponding carboxylic amides. The amines thus obtained were converted to 4-, 5-, and 6-acetaminobenzofurans by acetylation. The 5-, 6-,-and 7-acetaminobenzofurans were also prepared by the cycliza-tion of 3-(p-, m-, and o-acetaminophenoxy)butanones. The 7-nitrobenzofuran was prepared by the Sandmeyer reaction of 7-aminobenzofuran. The four aryloxybutanones, 2,3-dimethyl-4- and -7-nitrobenzofurans, 4-amino-2,3-dimethylbenzofuran, and 2,3-dimethyl-4-, -5-, -6-, and -7-benzofurancarboxylic amides are new compounds.
Isomerization of Gomberg’s Trityl by Protonic Acids in Benzene
Authors: Takeuchi Hiroshi , Nagai Toshikazu , Tokura Niichiro 
Published: July 2006

Abstract
Gomberg’s trityl (1-diphenylmethylene-4-trityl-2,5-cyclohexadiene) (I) was isomerized by protonic acids such as HCl and phenol in benzene to form p-benzhydryltetraphenylmethane(II). p-(Benzhydryl-α-d)-tetraphenylmethane (III) was formed by the treatment of I with phenol-d. Ph3CH and Ph3CCl were treated under the same conditions, but II was not obtained. It was not formed either by the reaction of phenylazotriphenylmethane with phenol. This observation indicates that H+ adds to the terminal methylene of I to form the cyclohexadienyl cation followed by deprotonation to give II. Similarly, treatment of 1-(phenyl-p-tolymethylene)-4-(diphenyl-p-tolylmethyl)-2,5-cyclohexadiene (IV) with HCl in benzene afforded α,α,α′-triphenyl-α,α′-(di-p-tolyl)-p-xylene (V). The results support the view that Gomberg’s trityl is not hexaphenylethane but 1-diphenylmethylene-4-trityl-2,5-cyclohexadiene as suggested by Lankamp et al. (Tetrahedron Lett., 1968, 249). 1,1,2,2-Tetraphenylethane and 1,1,2,2-tetra-o-tolylethane not having the cyclohexadiene structure could not be isomerized by protonic acids (HCl and PhOH) in benzene. Thus, isomerization of this type is characteristic of the cyclohexadiene structure such as that of Gomberg’s trityl.
Studies of the Synthesis of Furan Compounds. XXIII. Cyclization Derivatives of 5-Nitro-2-furimidoylhydrazine
Authors: Hirao Ichiro , Kato Yasuhiko , Hayakawa Tsunetoshi , Tateishi Hiromichi 
Published: July 2006

Abstract
The reaction of 5-nitro-2-furimidoylhydrazine (I) with diacetyl or furil gave 3-(5-nitro-2-furyl)-5,6-disubstituted-1,2,4-triazine derivatives (IIa, b). Refluxing I in a large excess of ethyl orthoformate afforded 3-(5-nitro-2-furyl)-5-ethoxy-1,2,4-triazoline (III) and bis[3-(5-nitro-2-furyl)-1,2,4-triazolyl]methyl ethyl ether (IV). By heating with ethyl orthoformate, III was converted to IV. When III or IV was heated in diluted sulfuric acid, 3-(5-nitro-2-furyl)-1,2,4-triazole (V) was produced. The reactions of I with cyanogen bromide in refluxing methanol and with nitrous acid in diluted hydrochloric acid gave the corresponding 3-(5-nitro-2-furyl)-5-amino-1,2,4-triazole (VI) or -1,2,4,5-tetrazole (VIII) respectively. When heated in acetic anhydride, the VI afforded monoacetyl compound (VII), while the VIII yielded 5-(5-nitro-2-furyl)-2-methyl-1,3,4-oxadiazole (X). The structures of these compounds were discussed on the basis of their IR and NMR spectra.
Infrared Spectroscopic Study of Enol and Enol Derivatives Coordinated to Platinum(II) and Palladmm(II)
Authors: Wakatsuki Yasuo , Nozakura Shun-ichi , Murahashi hunsuke 
Published: July 2006

Abstract
The infrared spectra of [Cl2M Olefin]2 (olefin=vinyl alcohol, vinyl ethers, and their derivatives, M=Pt and Pd) have been studied in the 4000–100 cm−1 frequency region. A normal coordinate analysis of the coordinated vinyl alcohol indicated that the lone-pair electrons of oxygen conjugated with π-electrons of the double bond to some extent, even in the coordinated state. The coordination strengths of vinyl alcohol, vinyl ethers, and their derivatives have been examined by comparing the metal-olefin streching vibrations.
Derivatives of Ditriazinylamine
Authors: Fukushima Yoshiaki , Nohara Noboru , Hashida Y\={o}ji , Sekiguchi Shizen , Matsui Kohji 
Published: July 2006

Abstract
Various substituted ditriazinylamines were synthesized by the reaction of N,N-bis(4,6-dichloro-s-triazin-2-yl)amine, N,N-bis(4-chloro-6-phenyl-s-triazin-2-yl)amine, or 2-chloro-4-phenyl-s-triazin-2-yl-2′,4′-dichloro-s-triazin-2′-ylamine with nucleophilic reagents. The reaction of N,N,N-tris(4,6-dichloro-s-triazin-2-yl)amine with sodium methoxide was also examined. In this case, various products were obtained, depending upon the amount of sodium methoxide used. A Hammett plot of the substituent constants (∑σm) vs. the pKa′ or the imino proton shifts of the above-mentioned ditriazinylamines gives a linear relationship.
Reactions of Haloferrocenes. IV. The Condensation of Haloferrocenes with Various Carboxylic Acids in the Presence of Copper(I) Oxide
Authors: Sato Masaru , Lam Yau Ping , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
The condensation reaction of haloferrocenes with various carboxylic acids in the presence of copper(I) oxide was studied extensively. The reaction generally afforded the corresponding ferrocenyl carboxylates, along with a comparable amount of ferrocene. The change in the distribution of the reaction products was examined under various conditions in the reaction of bromoferrence with benzoic acid. From the discussion of the reaction mechanism, it was concluded that the ferrocenyl ester and ferrocene are produced through different active species. The reaction under proper conditions was found to be useful for the preparation of ferrocenyl esters.
Reactions of Haloferrocenes. V. The Formation of Ferrocenyl-triphenylphosphonium Perchlorate
Authors: Sato Masaru , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
The reaction of haloferrocene with tetrakis(acetonitrilo)copper(I) perchlorate in nitromethane gave a 35% yield of biferrocenyl. The addition of triphenylphosphine to the reaction system causes a remarkable change in the reaction and gives ferrocenyltriphenylphosphonium perchlorate in a good yield. The scope of the formation of the quaternary salt was investigated in comparison with the corresponding reactions in the benzene series. It was found that the ligands coordinated in the intermediate copper(I) complex strongly affect the reaction. The mechanism of the formation of ferrocenyltriphenylphosphonium salt is also discussed.