bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Insertion Reaction of Propylene into Metal-Ethyl Bonds in the Ziegler-Natta Catalyst
Authors: Takegami Yoshinobu , Suzuki Toshimitsu , Okazaki Takuya 
Published: July 2006

Abstract
The insertion reaction of propylene into metal-ethyl bonds in TiCl4-AlEt3, TiCl3-AlEt3, TiCl3-AlEt2Cl, and TiCl3-ZnEt2 catalyst systems was studied. The insertion products were converted to the corresponding hydrocarbons by methanolysis, and then analysed by gas-liquid chromatography. From these hydrocarbons, the following three metal alkyls were considered to be formed in the reaction system;
(Remark: Graphics omitted.)
These metal alkyls were formed in the solid phase of the catalyst at first and were then transferred to the liquid phase of the catalyst. The amount of the metal alkyls formed in the reaction system was dependent on the catalytic system used. The active polymerization system TiCl3-AlEt3 gave a very small amount of metal alkyls, but the less active TiCl3-ZnEt2 and -AlEt2Cl systems gave a much greater quantity of the metal alkyls, (I) and (III). In the case of the TiCl4-AlEt3 system, metal alkyl formation was much affected by the Al/Ti molar ratio and the reaction time. Finally, it was concluded that the metal alkyls formed in the system were connected to the polymerization of propylene.
The Ionic Telomerization of Diene Compounds. IV. The Cationic Telomerization of Butadiene with Its Hydrobromides
Authors: Asahara Teruzo , Kise Hideo 
Published: July 2006

Abstract
The cationic telomerization of butadiene with its hydrobromides (1-bromo-2-butene and 3-bromo-1-butene) in the presence of metal halide was investigated. It was found that the molecular weights of the telomers depend on the conversion of the telomerization, initial bromide/ butadiene ratio and the solvent used. When halogenated hydrocarbons were used as solvents, telomers with high molecular weights and low unsaturations were obtained. On the other hand, the telomerizations in ether solvents gave telomers with low molecular weights, which contained appreciable amounts of the simple adducts of butadiene and bromobutene. The infrared spectra of the telomers suggested that the addition of butadiene occurred mainly at 1,4-position. On the basis of the analyses of the telomers, the reactivities of the carbonium ion to the basic species which were present in the reaction system were estimated.
Deuteron Magnetic Resonance Study in Co(ND3)6Cl3
Authors: Ito Takeshi , Chiba Takehiko 
Published: July 2006

Abstract
Deuteron quadrupole coupling tensors in Co(ND3)6Cl3 were determined at various temperatures. The observed quadrupole coupling shows that Co(ND3)63+ ions execute a rapid isotropic reorientation at high temperatures (above 320°K for one of the sites (the 4f sites) and above 190°K for another (the 2e sites), while at low temperatures (below 190°K for the 4f sites, and 170°K for the 2e sites), only a C3 axis reorientation of the ligand ND3 groups is present. The deuteron resonance spectra clearly show that Co(ND3)63+ ions in the 4f sites begin to reorient about one of the three C4 axes at intermediate temperatures (about 240°K). On the basis of the orientation of quadrupole tensors, probable orientations of Co(ND3)63+ ions in the 4f sites in the crystal are proposed. Additional measurements of the proton resonance on a single crystal of Co(NH3)6Cl3support the results obtained from the deuteron resonance. To obtain the reorientation rates and the activation energies of these reorientational motions, the deuteron resonance line width at the 4f sites is measured at various temperatures and at various crystal orientations. From the temperature dependence of the line width, the presence of two cations with slightly different rates at the 4f sites is suggested. However, because of the limits set by the various experimental conditions, reliable values of the reorientation rates and activation energies could not be obtained.
Oxygen Exchange Reaction of Sulfoxides in Dinitrogen Tetroxide
Authors: Kunieda Norio , Sakai Kazuo , Oae Shigeru 
Published: July 2006

Abstract
Sulfoxides are known to undergo concurrent oxygen exchange and racemization reactions with various reagents (Bull. Chem. Soc. Japan, 41, 1025 (1968)). Especially well studied are the oxygen exchange reactions in acid media. We have found a similar concurrent oxygen exchange and racemization reaction of sulfoxides with liquid dinitrogen tetroxide. The pseudo first order reaction rates of both oxygen exchange and racemization reactions have been determined using both optically active and 18O-labeled sulfoxides. The kex⁄krac value was found to be unity, and the polar effect of substituents on the rates of oxygen exchange of substituted diphenyl sulfoxides was found to be considerably large, and correlated with σ+ values with ρ=−1.30. From these results a plausible mechanism for this reaction has been discussed.
Photochemistry of β-Acylacrylic Acids and Their Esters
Authors: Sugiyama Noboru , Kataoka Hiroshi , Kashima Choji , Yamada Kazutoshi 
Published: July 2006

Abstract
The irradiation of methyl trans-β-acetylacrylate (I-A) in methanol or acetone or without any solvent gave the cis-isomer (I-B). On the contrary, the irradiation of the free acid of I-A, trans-β-acetylacrylic acid (II-A), in methanol or without any solvent gave the angelica lactone, 5-methyl-5-hydroxy-2-oxo-2,5-dihydrofuran (II-C). The irradiation of trans-β-pivaloylacrylic acid (III-A) in methanol also afforded the angelica lactone, 5-t-butyl-5-hydroxy-2-oxo-2,5-dihydrofuran (III-C). The reaction route from a cis-isomer to an angelica lactone was explained in terms of the inductive effect.
The α Effect. Aminolysis on a Saturated Carbon Atom
Authors: Oae Shigeru , Kadoma Yoshihito , Yano Yumihiko 
Published: July 2006

Abstract
The rates of aminolyses of methyl, isopropyl, allyl and benzyl iodides have been determined in acetonitrile. Bases used were hydrazine, morpholine, imidazole and piperidine. The rates of all the aminolysis reactions can be correlated nicely with the basicities. Hydrazine also did not show any positive deviation from the Brφnsted plots. This fact suggests that the α-effect is not operative in these displacement reactions on the saturated carbon atom.
Amino-quinoid Polymeric System. The Preparation of a Polyester Containing 2,5-Diamino-p-benzoquinone Nuclei and Its Crosslinking
Authors: Kumanotani Ju , Sugita Kazuyuki , Kazama Seiji , Yoshikawa Toshio 
Published: July 2006

Abstract
A polyester containing 2,5-diamino-p-benzoquinone nuclei was prepared by the polycondensation of 2,5-bis(ω-carboxyl-pentylamino)-p-benzoquinone with polyethylene glycol 400 at 160°C, 170°C and 180°C. At 160°C the esterification was brought about easily without gelation, giving an amino-quinoid polyester (prepolymer), but above 170°C an unexpected gelation was observed. The amino-quinone nuclei incorporated in the polyester thus prepared were confirmed by NMR spectroscopy. To make clear the influence of the amino-quinone nuclei upon the gelation, the thermal reactions of the model compounds, the above amino-quinoid dibasic acid, and its ethyl ester were investigated by means of IR spectroscopy and chemical analysis. It was concluded that the hydrogen atoms in the amino-groups of the quinone move to the oxygen atoms and that the resulting hydroxy groups combine with each other to form an ether bond as a result of dehydration. When the prepolymer prepared at 160°C was heated at 170°C for 4 hr with p-toluenesulfonic acid (5% by weight) or at 180°C for 8 hr without the acid catalyst, there was obtained an infusible and insoluble film which made crosslinkage as shown in the above mechanism.
Electroless Nickel Plating from Acid-acetate Baths Containing Hypophosphite as a Reducing Agent
Authors: Ogawa Kin’ya 
Published: July 2006

Abstract
The properties of acid-acetate baths containing hypophosphite as a reducing agent were studied in an attempt to obtain an electroless nickel deposit; further, the protective property of such deposits with phosphorus contents of 4 to 13% was investigated. The hypophosphite utilization efficiency for the deposition of electroless nickel was found to be 0.33; the deposition rate indicates a first-order dependence on hypophosphite, but it is independent of nickel concentration, within the limits specified in the range of suitable conditions. The phosphorus content of the deposits increases with a decrease in the pH value of the bath and with an increase in the initial concentration of hypophosphite, but it is independent of that of nickel. An electoless nickel with a high phosphorus content affords more protection against metallic bases.
Effect of Additives in the Radiolysis of Gaseous Ammonia at High Densities
Authors: Nishikawa Masaru , Kuroda Kazufumi , Matsuura Niro 
Published: July 2006

Abstract
The effect of additives and density on the radiolysis of ammonia at 140°C was studied over the density range 0.07 to 0.13 g/cc. The observation of a sharp decrease of G values in the radiolysis of pure ammonia at d∼0.1 g/cc confirmed the result reported by Toi et al. (Radiation Res., 17, 399 (1962)). The yield of hydrogen in the presence of ∼1.5 mol% C3H6 was practically independent of density at G=0.65 over the density range studied. G(H2) in the presence of C3H8, estimated by extrapolation to zero propane concentration, was also constant at G\simeq5.7 at d\simeq0.07 and 0.13 g/cc. These observations were discussed in relation to the mechanism for depression of G values in the radiolysis of pure ammonia at higher densities.
Thermodynamic Properties and Phase Transitions of Thallous Cyanide Crystal
Authors: Matsuo Takasuke , Sugisaki Masayasu , Suga Hiroshi , Seki Syûzô 
Published: July 2006

Abstract
The heat capacities of TlCN crystal were measured from 15 to 300°K with an adiabatic calorimeter. Three regions of anomalously high heat capacity were discovered. Thermodynamic functions of the crystal were calculated by the graphical integration of the heat capacity data. 205Tl nuclear magnetic resonance was observed as functions of temperature and applied static magnetic field. Their second moment values could be interpreted in terms of the anisotropic chemical shift tensor.
Absorption Spectra and Circular Dichroisms of Metal Complexes. III. trans-Dihalogeno-bis-l-propylenediamine Complexes of Cobalt(III), Rhodium(III), Palladium(IV) and Platinum(IV)
Authors: Ito Haruko , Fujita Junnosuke , Saito Kazuo 
Published: July 2006

Abstract
Absorption (AB) and circular dichroism (CD) spectra of trans-[MX2(l-pn)2]n+ (where M=RhIII, PdIV- and PtIV-, and X=Cl− and Br−) have been discussed by comparing them with those of cobalt (III) complexes which had been studied extensively. A positive CD peak was observed at around the so called Ia band region of all the complexes studied except for trans-[PtBr2(l-pn)2]2+. A negative CD peak of this complex ion at 26000 cm−1 was assigned to be a split component of the Ia band. The AB peaks at 38000, 28600 and 31100 cm−1 for trans-[PtCl2(l-pn)2]2+, trans-[PdCl2(l-pn)2]2+ and trans-[PtBr2(l-pn)2]2+ respectively were assigned to pπ→dz2 charge transfer transition. An ion association band was observed for trans-[PtBr2(l-pn)2]Br2 in 1n hydrobromic acid.
Reactions of Metal Chelates. III. The Reactions of Bis(salicylaldehydato)copper(II) with Amides and Esters of Glycine and Glycylglycine
Authors: Hamada Kazuko , Ueda Hideo , Nakao Yasuo , Nakahara Akitsugu 
Published: July 2006

Abstract
The reactions of bis(salicylaldehydato)copper(II) in acidic, neutral and basic media with glycinamide, glycinester, glycylglycinamide and glycylglycinester have been systematically investigated. The reaction products have, in all cases, been isolated as crystals and characterized. As a result of this investigation, six new copper(II) chelates of Schiff bases derived from salicylaldehyde and glycine- or glycylglycine-amide have been obtained. The interrelation between those chelates has also been disclosed.
The Mixed Chromium(III) Complexes containing Acetylacetone and the Halogenations Thereof
Authors: Fujii Yuki , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The following three mixed chromium(III) complexes containing acetylacetone, which had a charge of from −1 to +1, were prepared: NH4[Cr(acac)(ata)]·H2O, [Cr(acac)(edda)]·2H2O and [Cr(acac)(edma)(H2O)]Cl·H2O. The halogenations at γ-position of the acetylacetonate ring were attempted in these three mixed complexes with NCS, NBS and ICl respectively in methanol and in acetic acid solutions, where NCS, NBS and ICl are abbreviated forms of N-chlorosuccinimide, N-bromosuccinimide and iodine monochloride, respectively. From an inspection of UV-spectra of the above halogenation reaction mixtures, all the three mixed complexes were confirmed to be halogenated at the γ-position of the acetylacetonate ring. Of these complexes, NH4[Cr(acac-Cl)(ata)]·\frac12H2O and [Cr(acac-Br)(edda)] were isolated as crystals from the reaction mixtures. IR-spectra measurement was also used to certify the halogen-substitution at γ-position in the above two compounds.
Synthesis of Vitamin B12 Model Compounds
Authors: Sasaki Tadashi , Matsunaga Fujinao 
Published: July 2006

Abstract
Bis(dimethylglyoximato)cobalt(III) complexes with the general formula: [CoX(DH)2BA] (X: CN−, NO2−, SeCN−, SCN−, Br−. D: dianion of dimethylglyoxime. BA: such biologically interesting bases as imidazole, benzimidazole, 5,6-dimethylbenzimidazole, pyridine, γ-picoline, 4-vinylpyridine, nicotinic acid, isoquinoline, 5-amino-4-imidazolecarboxamide, and 6-aminopurine) were prepared from dimethylglyoxime, the base, and an adequate cobalt (III) salt. The treatment of [CoCN(DH)2Imd] (Imd: imidazole) with boron trifluoride etherate afforded [Co(CNBF3)(DBF2)2Imd] in an 86% yield. The reduction of [CoCl(DH2)Imd] with sodium borohydride gave a labile [Co(I)H(DH)2Imd], which was directly converted with phenylacetylene into a stable [Co(III)(C6H5CH=CH)(DH2)Imd] in a 60% yield and into [Co(DH)2Imd]·H2O in a 30% yield. These products were structurally elucidated on the basis of their spectral data.
A Mechanistic Approach to the Electrolytic Reductive Dimerization of Acrylonitrile
Authors: Asahara Teruzo , Sen\={o} Manabu , Arai Takeshi 
Published: July 2006

Abstract
The electrolytic reductive dimerization of acrylonitrile was investigated extensively especially in order to obtain some mechanistic information. The essential point of this reaction exists in the selective formation of adiponitrile under relatively wide conditions and this cannot be explained by a normal kinetic treatment based on the reaction scheme which has been accepted as probable. The heterogenuity in acrylonitrile concentration in the reaction system is assumed and the kinetic formulas are modified. This treatment explains the experimental results very satisfactorily. In order to confirm this mechanistic scheme, the effects of temperature, pH and solvents on the yield of reaction products were examined. All the results are consistent with the proposed mechanism.
Studies of Acetothiolacetate
Authors: Motoki Shinichi , Sato Tadao 
Published: July 2006

Abstract
Ketene dimer reacted with mercaptan to give acetothiolacetate (I) in the presence of triethylamine. The ester I underwent a thermal condensation to give dehydroacetic acid (III), with the liberation of mercaptan, merely upon heating, and the reaction was effectively promoted in the presence of triethylamine. The ester I reacted with alkyl halide and acyl halide in dioxane to give α-alkyl and α-acylacetothiolacetate (II) respectively. Ethyl acetothiolacetate, ethyl α-methyl-acetothiolacetate, and ethyl α-acetylacetothiolacetate reacted with mercuric oxide at a low temperature to give diacetylacetone (VI), methyl ethyl ketone, and dehydroacetic acid (III) respectively.
The Structure of Copolymers of l-Proline with l-Glutamic Acid in Aqueous Solutions
Authors: Sakai Rume , Isemura Toshizo 
Published: July 2006

Abstract
Three copolymers of l-proline and l-glutamic acid were synthesized, and their equilibrium conformation in an aqueous solution was studied in relation to their composition. The molar ratios of the proline to the glutamic acid residues in the copolymers were about 1:3, 1:1, and 8:1. All the copolymers were soluble in water, as were poly-α,l-glutamic acid and poly-l-proline II. The conformational change was caused by the pH effect on proline-poor copolymers. Evidence was obtained for the possibility of the absence of such a helix as a right-handed poly-l-proline-I-helix in the copolymers examined. The conformation of Copoly-8:1 was not affected by the pH and was identified as the poly-l-proline-II-helix.
The Photoreaction of β-Benzoylacrylic Acid
Authors: Sugiyama Noboru , Kataoka Hiroshi , Kashima Choji , Yamada Kazutoshi 
Published: July 2006

Abstract
The product of the irradiation of trans-β-benzoylacrylic acid (1) in methanol was proved to be α-methoxy-β-benzoylpropionic acid (2), whose methyl ester was identified with an authentic material. On the other hand, the product of the irradiation of methyl trans-β-benzoylacrylate (5) was the cis-isomer. The photoreaction of 1 in various solvents, including EtOH, iso-PrOH, t-BuOH, ether, and AcOH, was examined from the standpoints of the cis-trans isomerization and alcohol addition. The rate of the photoreaction of 1 in methanol was determined, and a reasonable mechanism for the over-all reaction was proposed.
A Novel Method for the Synthesis of 1-Phenyl-2,3-dihydro-4-pyridones
Authors: Sugiyama Noboru , Yamamoto Makoto , Kashima Choji 
Published: July 2006

Abstract
The condensation of β-diketones, benzoylacetone (II), acetylacetone (III), or 6-phenyl-2,4-hexanedione (IV) with benzylidenaniline (I), in the presence of three moles of potassium amide in liquid ammonia, was found to give a dihydropyridone or an aminodiketone. Thus, the condensation of II with I afforded aminodiketone, 1-anilino-1,5-diphenyl-3,5-pentanedione (V), which cyclized to 2,3-dihydro-1,2,6-triphenyl-4-pyridone (IX) upon being treated with sulfuric acid. The condensation of III with I gave 2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (X) without any treatment with sulfuric acid. IV and I gave 2,3-dihydro-1,2-diphenyl-6-phenethyl-4-pyridone (XI) as the main product, with 3-benzyl-2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (XII) as a by-product.
An Improved Synthesis of N,β-Dimethylleucine and the Resolution Thereof
Authors: Kotake Hiroshi , Saito Tomoo , Okubo Kazuo 
Published: July 2006

Abstract
A diastereoisomeric mixture of racemic β-methylleucine was synthesized by the condensation of 2-benzyl-4(5H)-imidazolone with the methyl isopropyl ketone, followed by catalytic hydrogenation and hydrolysis. The separation of the mixture into threo-β-methyl-Dl-leucine and erythro-β-methyl-Dl-leucine was mainly achieved by fractional crystallization from water. The resolution of each diastereoisomer was also accomplished through salt-formation with (−)- and (+)-ephedrine alternately before or after the methylation of the amino group. The specific rotation and the NMR and IR spectra of one isomer, threo-N,β-dimethyl-l-leucine, corresponded closely with those reported for dimethylleucine isolated from nature.
Characteristic Chemical Constitution of Pitch Materials Suitable for the MP Carbon Fiber
Authors: Otani Sugio , Yokoyama Akira 
Published: July 2006

Abstract
Pitch materials suitable for the MP carbon fiber were prepared from petroleum asphalt, coal tar pitch, and polyvinylchloride. The present investigation was undertaken to clarify the characteristic chemical constitution of each suitable pitch material and to define the significance of the special treatment required to prepare the pitch materials. The suitable pitch materials are generally composed of several structural units with aromatic fused rings and more or less alkyl side chains. The suitable pitch material finally obtained from the petroleum asphalt is characterized by a relatively high molecular weight and many quite long alkyl side chains. Special treatment is required to increase the aromaticity and the removal of the low-molecular-weight component. The suitable pitch material from the coal tar pitch is characterized by aromatic fused rings of the condensed type and only a few alkyl side chains, such as, the methyl group. The most desirable effect of the treatment is to accelerate the condensation between molecules without increasing the insoluble matter and to remove the low-molecular-weight component. The results concerning the polyvinylchloride pitch lend some support to the scheme suggested before.
Mössbauer Effect of 119Sn in Molecular Complexes of Tin(IV) Chloride with Several Aromatic Compounds
Authors: Ichiba Sumio , Mishima Mitsuo , Negita Hisao 
Published: July 2006

Abstract
The Mössbauer spectra of molecular complexes of tin(IV) chloride with some oxygen-containing aromatic compounds, such as hydroxybenzaldehydes and cinnamic acid, were investigated. Most of these complexes show the quadrupole splitting resulting from the addition of aromatic molecules to tin(IV) chloride, although in some cases broad absorption curves are observed. The isomer shifts of these complexes are 0.25—0.45 mm/sec, much smaller than that of tin(IV) chloride itself. These values are almost the same as those of the complexes of tin(IV) chloride with aliphatic compounds. From these results, the bond nature and structures of these complexes, which had not previously been studied, were discussed in some detail.
The Heat of Immersion of Ferric Oxide in Water
Authors: Morimoto Tetsuo , Katayama Noriko , Naono Hiromitu , Nagao Mahiko 
Published: July 2006

Abstract
Four kinds of ferric oxide (α-Fe2O3) which differ in origin and history have been used for measurements of the surface area, the water content, and the heat of immersion in water. Two cases have been discovered; in one there appears a maximum in the plot of the heat of immersion against the pretreatment temperature according to the origin of the sample, but in the other a maximum does not appear. The heavy hydration treatment carried out prior to the immersion measurements raises the value of the heat of immersion in water, but it has no serious effect on the heat of surface hydration calculated therefrom, as in the case of TiO2. The average value of the latter was 11.3 kcal/mol H2O.
The Oxovanadium(IV) Complexes of Schiff Bases Obtained from Substituted Salicylaldehydes and Alkyl Amines
Authors: Yamada Shoichiro , Kuge Yoshio 
Published: July 2006

Abstract
Many new oxovanadium(IV) complexes (abbreviated as VO(X-sal.R)2) of Schiff bases obtained from substituted salicylaldehydes and alkylamines have been synthesized as crystals, where X=H and 3-CH3O and R=CH3, C2H5, n-C3H7, n-C4H9, iso-C3H7, CH(CH3)(C2H5), CH2CH-(CH3)2 and cyclohexyl. Since all these complexes show similar electronic spectra, it is considered that they take an essentially similar configuration, that is, a square-pyramidal one in the solid state and in chloroform, even for R=α-branched alkyls. This result is different from that of the copper (II) complexes. It is also concluded that these oxovanadium(IV) complexes, when dissolved in pyridine, take up one pyridine molecule to form a six-coordinated species. The configuration of the pyridine solvate depends upon R.