bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetic Studies of Thermal Decomposition Reactions of Metal Complexes. Hexammine- and Halogenopentamminecobalt(III) Complexes
Authors: Tanaka Nobuyuki , Nagase Kenzo 
Published: July 2006

Abstract
The thermal decomposition reactions of amminecobalt(III) complexes in solid state were studied mainly by the polarographic, the manometric and the infrared spectroscopic methods. The decomposition processes of [Co(NH3)6]Cl3, [Co(NH3)6]Br3, [Co(NH3)6]I3, [CoCl(NH3)5]Cl2, [CoBr(NH3)5]Cl2, [CoCl(NH3)5]Br2 and [CoBr(NH3)5]Br2 in vacuo, in air atmosphere and in sealed tube were investigated. In all cases, the decomposition of these complexes was initiated by electron transfer from an outer-sphere anion or a ligand to the central cobalt(III) cation. The reaction processes and products were found to be much different with the different environments, but little different with the different halide ions. The rate constants, frequency factors and activation energies for the electron transfer reactions were obtained.
The Infrared Spectra and Some Properties of Tris-(acetylacetonato) Lanthanide(III) Complexes
Authors: Misumi Seizo , Iwasaki Noriko 
Published: July 2006

Abstract
The infrared spectra of tris-(acetylacetonato) complexes of praseodymium(III), neodymium-(III), europium(III), gadolinium (III), dysprosium(III), and erbium(III) have been measured in the range between 4000 and 100 cm−1 in order to obtain information about the nature of lanthanide metal-oxygen bond; some properties of these complexes were studied, also. The calculated frequencies and assignments were used to elucidate the complex spectra and to show the relations between the calculated force constants and some physicochemical properties. Although the molecules of each complex were 1 : 3 complexes, the calculation of the vibrational frequencies was made by using a simplified model of the 1 : 1 complex (C2v), because it may be supposed that this tris-(acetylacetonato) complex does not always have a regular octahedral symmetry in spite of the composition of Ln(acac)3. The calculated frequencies were in good agreement with the observed ones; the lanthanide metal-oxygen stretching vibrations were found at 420–432 cm−1 (A1-ν5) and 304–322 cm−1 (B1-ν14). The lanthanide metal-oxygen stretching force constant increases with an increase in the atomic number, while the corresponding C=O stretching frequency (A1-ν1) decreases in the same order. For example, the values of K(Pr–O) and K(Er–O) are 2.10 and 2.29 md/Å respectively. As the result of the lanthanide contraction, the force constant of the lanthanide metal-oxygen bond increases with a decrease in the M–O bond length, thus increasing the stability constant, log β, and slightly increasing the electronegativity.
The Yields of Radioactivities Induced by (γ, n) Reactions with 20 MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Nomura Koichi , Saito Tatsuya 
Published: July 2006

Abstract
The yields of radioactivities resulting from the (γ, n) reactions on 37 elements covering the periodic table have been determined by means of 20 MeV linear accelerator bremsstrahlung and gamma-ray spectrometry. The yield values, as measured in the number of photodisintegrations per mole per roentgen for each of the (γ, n) reactions, increase in the main regularly with atomic number from 103 through 107 order of magnitude. Anomalously small yield values are obtained in the irradiation of the nuclides with neutron or proton number of the magic numbers. The present results permit studies of general behavior of the photoneutron reactions and of the application of their products to the photoactivation analyses of many elements distributed throughout the periodic table.
The Hunsdiecker Reaction of Silver Acrylate and Methacrylate
Authors: Furukawa Shu , Naruchi Kiyoshi , Matsui Shigetake , Yuuki Michio 
Published: July 2006

Abstract
The Hunsdiecker reaction of silver acrylate and methacrylate has been investigated; 1, 1, 2-tribromoethane was obtained from the former, and bromoacetone from the latter. Since bromoacetone has also been obtained by the reaction of 2-bromopropene-l with acetyl hypobromite, it is conceivable that, in the case of the Hunsdiecker reaction of silver methacrylate, methacryloyl hypobromite (the intermediate of the Hunsdiecker reaction) oxidized 2-bromopropene-l (the primary product of the Hunsdiecker reaction) to bromoacetone, with an accompanying rearrangement of the bromine atom.
Reactions of Triethylaluminum with Electron Donors
Authors: Takashi Yûkichi 
Published: July 2006

Abstract
As a study of the roles of the electron-donor compounds in the three-component Zieglertype catalysts, the reactions of triethylaluminum with various electron donor compounds, e. g., triethylamine, pyridine, diethyl ether, tetrahydrofuran, dioxane, and triethylstibine, have been investigated by means of the proton magnetic resonance. The internal chemical shifts between the α- and β-protons of the substituent groups bound to key atoms in the reaction mixtures have indicated that (1) each donor gives only one type of complex which is ordinarily expected, and (2) the coordination of the donor to triethylaluminum lowers the electronegativity of the aluminum atom. Qualitative information about the ligand exchange reactions of the donor complexes has also been obtained. All the complexes obtained showed remarkable electrical conductivities, indicating ionic structures.
Kinetic Studies of Solvolysis. XIII. The Solvolyses of Optically-active α-Phenylethyl Chloride in Binary Mixtures of Phenol and Water—The Sn1 Hydrolysis with the Retention of the Configuration
Authors: Okamoto Kunio , Hayashi Masayuki , Komatsu Koichi , Shingu Haruo 
Published: July 2006

Abstract
The competitive Sn1 hydrolysis and Sn1 phenolysis of optically-active α-phenylethyl chloride in aqueous phenols (75 to 90 wt% phenol) give partially-retained α-phenylethyl alcohol and α-phenylethyl phenyl ether in the presence of added triethylamine at 14 and 30°C. The extent of the retention of the configuration is almost independent of the reaction temperature, whereas it shows a tendency to increase from 13 to 23% for the alcohol and from 5 to 20% for the ether with an increase in the phenol concentration. A predominant four-center (Sni-like) attack of a water molecule, with the assistance of a specific solvation of phenol molecules, has been suggested as a possible interpretation for the unusual hydrolysis with a retained steric course for this simple secondary alkyl system. In connection with the nature of the specific solvation of phenol molecules, the applicability of the concept of the back-side shielding of the Sn1 ion-pair intermediate by a phenol molecule has been discussed.
The Redistribution Reaction of Ethyl Groups and Chlorine Atoms in the Ethylaluminum Chloride + Ether System
Authors: Tarao Ryokichi , Takeda Saburo 
Published: July 2006

Abstract
The redistribution reactions of ethyl groups and chlorine atoms in the 2AlEtnCl3−n+ether system were studied by the Raman spectroscopic method. It was found that the reaction of AlEtCl2 with Et2O (molar ratio, 2:1) gave rise to AlEt2Cl and AlCl3·Et2O, although not quantitatively. On the contrary, the reaction of AlEt2Cl with Et2O (molar ratio, 2:1) did not produce any AlEt3 or AlEtCl2·Et2O at all. These and several related observations demonstrate that, by the reaction between AlEtnCl3−n and AlEtmCl3−m·Et2O (n, m=0, 1, 2, 3), AlEt2Cl is preferentially produced as long as there is any possibility of its formation.
Formation of Complexes from Azobenzenes and Cyclopentadienyl Cobalt Derivatives
Authors: Joh Takashi , Hagihara Nobue , Murahashi Shunsuke 
Published: July 2006

Abstract
New complexes (III) have been found to be formed in the reaction between aromatic azo compounds and cyclopentadienyl cobalt derivatives. The same complexes have also been obtained from the reaction of o-quinonediimine or o-phenylenediamine derivatives with cyclopentadienyl cobalt dicarbonyl. These complexes reacted with carbon monoxide to yield benzimidazolone derivatives, and with hydrogen to give o-phenylenediamine derivatives. The structure of the complexes has been formulated on the basis of the infrared spectra, the proton magnetic resonance, and chemical evidence.
Thermische Zersetzung von Benzoylphenylacetylperoxyd in Lösung
Authors: Suehiro Tadashi , Tsuruta Hideki , Hibino Shuji 
Published: July 2006

Abstract
Benzoylphenylacetylperoxyd zersetzt sich in Benzol anscheinend nach 1. Ordnung und bei 25°C erhält man Geschwindigkeitkonstant, Aktivierungsenergie und Aktivierungsentropie je (2.05±0.04)×10−4 Sek−1, 21.7 kcal·Mol−1 und −5.0 cal·Grad−1. Die Bildung von freien Radikalen während der Zersetzung beträgt, nach der spektroskopischen Bestimmung mittels Diphenylpikrylhydrazyl, erst unter 10 Mol%. Produktenanalyse der Umsetzung vom Peroxyd in Lösung durch Gaschromatographie zeigt das Auftreten von Benzyl-Kation und die monomolekulare Entstehung von Benzoesäurebenzylester, und durch Infrarot-Spektrum, die Bildung von Benzylkohlensäurebenzoesäureanhydrid. Die Zersetzung wird beschleunigt durch Säure unter gleichzeitiger Zunahme des Produktes Diphenylmethanderivates in Aromaten mit Elektron-Donator Substituent, und auch durch die Poläritat von Lösungsmitteln. Alle diese bedeuten, dass Peroxyd zerfällt in keiner normaler Weise der homolytischen Spaltung von O–O Bindung, sondern zersetzt sich in drei parallel laufenden Reaktionen 1) zum Benzyl-Kation, 2) zum Benzoesäurebenzylester und 3) zum Benzylkohlensäurebenzoesäureanhydrid in ungefähr gleichen Massen.
The Structural Change in Zinc Oxide in the Process of Mechanical Treatment
Authors: Takahashi Hiroshi , Tsutsumi Kazuo 
Published: July 2006

Abstract
The structural change in zinc oxide by mechanical treatment was studied. In the process of the mechanical treatment of zinc oxide, the crystallite size and the lattice distortion as measured by the X-ray diffraction method, the specific surface area as measured by the BET method, and the density as measured by a pycnometer changed monotonously with the treatment time. Such monotonous changes correspond to a primary structural change in zinc oxide.
ESR Study of the Ion Pairs of the Phthalonitrile Anion with Alkali Metals
Authors: Nakamura Kazuo , Deguchi Yasuo 
Published: July 2006

Abstract
From the ESR spectroscopic point of view, there are two distinct species of ion pairs of the phthalonitrile anion with the lithium ion in ethereal solvents. One corresponds to the locating of the cation in close proximity to a cyano group. Its ESR spectrum exhibits the loss of twofold symmetry in the spin distribution on the anion (spectrum I) or an alternating line width (spectrum II), depending on the transfer rate of the cation between the two cyano groups. The other species refers to the locating of the cation probably in the spacing between the two cyano groups. The appearance of its spectrum (spectrum III) is similar to that of the free anion. The DME or THF solution gives spectrum II; the ethyl ether solution, spectrum III, and the THP or MeTHF solution, the superposition of spectrum I or II upon III. A similar two species are found in the sodium ion pair. The negative spin density at the meta-carbon atom to the cyano group where the cation is located has been found. The solvent and the temperature effects on the alkali metal splittings, a semi-quantitative treatment of the alternating line width, and the variations in the proton and nitrogen coupling constants are also described.
The Addition Reactions of Ethanol to Ethylene Induced by Gamma-ray Irradiation in the Gaseous Phase. II. A Kinetic Analysis of the Results
Authors: Kurihara Hirondo , Hotta Hiroshi 
Published: July 2006

Abstract
In order to analyze the results obtained in Part I (H. Hotta and H. Kurihara, Bull. Chem. Soc. Japan, 40, 714 (1967)), a general kinetic expression for the system which involves side chain reactions is derived by a modification of the Gale and Wagner method (J. Am. Chem. Soc., 86, 4531 (1964)) on the basis of the G-values without the steady-state approximation. By the use of this expression, the chain transfer constants are found to be C1′=0.093 and C2′=0.074 in the gaseous phase, and about C1′=0.007 in the liquid phase. These values are compared with the reported chain transfer constants for related systems.
Thermodynamics of the Hydroxymethylation of Melamine and Urea with Formaldehyde
Authors: Sato Kenji 
Published: July 2006

Abstract
The hydroxymethylation of melamine and urea with formaldehyde in an aqueous solution was studied thermodynamically. The entropy, enthalpy, and free energy of activation for the early stages of the reaction, i. e., the formation of mono-methylol derivatives, and also the changes in the entropy, enthalpy, and molecular heat, etc., were determined in connection with the functionalities. It was confirmed that no marked differences exist between the rate constant of melamine and that of urea, but that the ΔS\eweq and ΔH\eweq values of urea are considerably smaller than the respective values of melamine. Prominent differences do exist between ΔS and ΔH\eweq, the ΔS\eweq and ΔH\eweq terms of melamine amount roughly to 105 times and 105 times those of urea respectively, regardless of the functionalities. These results imply a conspicuous difference between their reaction mechanisms, a difference which is explicable in terms of the characteristics of their amino-group nitrogen. Besides, the solvent effect of dimethylsulfoxide in the hydroxymethylation of melamine was investigated; it will be discussed in connection with the solvation.
Extraction of Scandium(III) with Tri-n-butyl Phosphate from Chloride Solutions
Authors: Morris D F C , Sutton K J 
Published: July 2006

Abstract
The distribution of scandium(III) between tri-n-butyl phosphate and aqueous solutions containing chloride has been measured using 46Sc as a tracer. The extraction of anionic scandium chlorocomplexes seems to be unimportant in the systems studied and it appears that different solvates of the trichloride ScCl3 can exist in tributyl phosphate extracts.
Studies of the Complex Formation between Uranium and Thiosalicylic Acid
Authors: Kumar A N , Nigam H L , Katyal M 
Published: July 2006

Abstract
Orange-yellow coloured complexes formed by the interaction of uranium and thiosalicylic acid in 40% ethanol have been investigated by spectrophotometric, potentiometric, and magnetic susceptibility measurements. Spectrophotometric studies reveal that a 1 : 1 complex is mainly formed below pH 4.5, while at higher pH’s (5.5) a 1 : 2 (metal : ligand) complex is mainly formed. Magnetic susceptibility measurements point towards the diamagnetic character of the complexes. The stereochemical configuration of the complex ions has been discussed.
Simple Malonate and Maleate Complexes of Oxovanadium(IV)
Authors: Sathyanarayana D N , Patel C C 
Published: July 2006

Abstract
Oxovanadium(IV) malonate tetrahydrate, VO(malon)·4H2O and oxovanadium(IV) maleate dihydrate, VO(mal)·2H2O are prepared and characterised. Magnetic moments agree with quadrivalent vanadium. The differential thermal analysis and infrared spectra of both the complexes have been studied. Molar conductance, molecular weight by cryoscopic method and the electronic spectrum of the malonate have also been obtained. A comparison of oxalate, malonate and maleate complexes of the type VO(LL)·x H2O (LL, being one of the bidentates) is attempted to arrive at a series from cryoscopic data, thermal decomposition temperature and vanadium-oxygen stretching frequency. The series obtained showing the ‘stability’ is: oxalate&gt;malonate&gt;maleate and is expected to be the same as the naphelauxetic series.
The Chemistry of Protactinium. III. A Study of the Sulfate Complex of Protactinium(V) by the Solvent Extraction Technique Using TTA as the Chelating Agent
Authors: Mitsuji Toshikazu , Suzuki Shin 
Published: July 2006

Abstract
The behavior of pentavalent protactinium in sulfuric acid solutions was investigated by paper electrophoresis and by the TTA-benzene extraction method. From the results of this investigation, it is recognized that the Pa(OH)2(SO4)+ ion exists predominantly in dilute sulfuric acid solutions (pH 0.4–2.2), and that the complexing reaction of pentavalent protactinium by the sulfate ion may proceed as;
Pa(OH)4++2H++SO42−\ightleftarrowsPa(OH)2(SO4)++2H2O.
The stability constant of Pa(OH)2(SO4)+ was also determined by the solvent extraction method to be 6.4 at an ionic strength of 1.38.
Some Aspects of Solid State Reactions between Oxides
Authors: Yamaguchi Goro , Tokuda Toshio 
Published: July 2006

Abstract
Solid state reactions in air between two oxide pieces of a single crystal or a polycrystal were conducted and observed; the couples were MgO and Al2O3,ZnO and Al2O3,MgO and Fe2O3,MgO and Cr2O3, MgO and SiO2, MgO and TiO2, and CoO and TiO2. In all the reactions except the MgO-Fe2O3 reaction, the two pieces were easily separated after the reaction. Moreover, in all the reactions except the MgO-SiO2 reaction, the reacted substances adhered selectively to one of those two pieces. The host crystals (to which the reacted substances adhered) were Al2O3 in the cases of MgO-Al2O3 and ZnO-Al2O3, Fe2O3 in the case of MgO-Fe2O3, MgO in the case of MgO-Cr2O3, and TiO2 in the cases of MgO-TiO2 and CoO-TiO2. In the reaction between MgO and SiO2, 2MgO·SiO2 adhered to MgO and MgO·SiO2 adhered to SiO2. In the reactions of MgO-TiO2 and CoO-TiO2, three layers of different compounds were formed, all adhering to TiO2. The mechanism of the diffusion of ions through the reacted layer was hard to determine in detail. It was pointed that the investigators must be careful in confirming the field of diffusion and in discriminating the diffusion through the diffusion field of the lattice from that through the surface and the space. Only in the cases of MgO-Al2O3 and ZnO-Al2O3 was the mechanism clearly determined to be the counter diffusion of cations through the spinel lattice formed, by means of a natural mark.
Infrared Spectra and Molecular Vibrations of Ethylene Glycol and Deuterated Derivatives
Authors: Matsuura Hiroatsu , Miyazawa Tatsuo 
Published: July 2006

Abstract
The infrared spectra of ethylene glycol and ethylene glycol-d2 have been measured in the liquid and crystalline states in the region 4000—300 cm−1. The infrared and Raman spectra suggest that ethylene glycol molecule takes only the gauche conformation as to the C-C bond in both states (the likely models are TGT, TGG and GGG). To establish the vibrationarassignments, the normal coordinate treatments of ethylene glycol and its three deuterated derivatives have been carried out for these models by the use of GF matrix method. The modified Urey-Bradley force field has been used and the force constants have been transferred from similar molecules. The potential energy distributions have also been calculated and the nature of the observed infrared bands and Raman lines in the liquid state has been discussed. The empirical assignments of the methylene rocking modes by the previous investigators have been revised by the present normal coordinate analyses.
Structure of Dimethylthallium Compounds Soluble in Non-polar Solvents
Authors: Kurosawa Hideo , Yasuda Kiyoshi , Okawara Rokuro 
Published: July 2006

Abstract
Several dimethylthallium derivatives were studied by means of a study of their IR and NMR spectra and by measurements of their physical properties. These new compounds, (CH3)2· TlSC6H5, (CH3)2TlOC6H4Cl-o, and (CH3)2Tl[B(C6H5)], are described. By correlation with earlier reports, it is possible to classify dimethylthallium derivatives into two groups according to the nature of the hybridization of the Tl-bonding orbitals. The experimental results can be interpreted in a straightforward and consistent manner.
The Photochemical Reaction of Ethylene Glycol with Ferric Chloride-Pyridine Complex
Authors: Inoue Hiroo , Tamaki Kentaro , Komakine Nobuyuki , Imoto Eiji 
Published: July 2006

Abstract
The photochemical reaction of ethylene glycol with ferric chloride-pyridine complex are carried out under a nitrogen atmosphere with 100 W mercury lamp at room temperature. Glyoxal, formaldehyde, acetaldehyde and water are obtained as the main products. When the molar ratio of pyridine to ferric chloride is below 1–2, the amounts of glyoxal and formaldehyde produced increase with increasing the amount of pyridine, though that of acetaldehyde decreases. In the process, Fe(III) is photo-reduced to Fe(II). Thus, the remarkable effect of pyridine on the photochemical reaction is observed. From these results, the mechanisms of the action of the excited Fe(III) in the presence and absence of pyridine are assumed here.
Reactions of Allenes. I. The Synthesis of Unsaturated Monocarboxylic Esters by the Carboxylation Reaction of Allenes; Reaction Conditions and Products
Authors: Kunichika Sango , Sakakibara Yasumasa , Okamoto Tadashi 
Published: July 2006

Abstract
The carboxylation reaction of propadiene and 1,2-hexadiene with carbon monoxide and methanol in the presence of a catalyst was studied. Propadiene was carboxylated to give methyl methacrylate in a fairly good yield (62% based on the propadiene consumed) by the use of a catalyst composed of nickel carbonyl and methacrylic acid or water under a relatively low pressure. A small amount of methyl vinylacetate was also present. The predominant side reaction was a polymer formation reaction. The carboxylation of 1,2-hexadiene, however, did not proceed smoothly, and a great amount of tarry materials was obtained. The carboxylation products obtained in low yields (max. 15%) were exclusively the materials formed by a carbonyl attack on the central carbon of the allenic structure, that is, methyl trans-2-methyl-2-hexenoate and methyl 2-butyl-2-propenoate.
Homolytic Chlorination of Aliphatic Compounds. I. Photochlorination of Chloroethanes
Authors: Migita Toshihiko , Kosugi Masanori , Nagai Yoichiro 
Published: July 2006

Abstract
The effect of the structure on the rate of hydrogen abstraction from chloroalkanes by a chlorine atom has been investigated by carrying out the competitive photochlorination of eight different chloroethanes in the presence of 2,2-dichloropropane to which the relative site reactivities have been referred. The results show that the successive introduction of a chlorine sub-stituent at the 1-position decreases the reactivity of the 2-position, but that, in some cases, it increases that of the 1-position. A linear free-energy relationship is found to exist between the reactivities of the R group in R-R′ (R=methyl, chloromethyl or dichloromethyl; R′=methyl, chloromethyl, dichloromethyl or trichloromethyl) and Taft’s σ* constants for the R′ group. These facts are elucidated in terms of the inductive and resonance effects of the substituent groups.
Studies on Antibiotics and Related Substances. XXIX. Syntheses of 2-Acetamido-5-oxo-6-heptenoic Acid and 2-Acetamido-4-oxo-5-hexenoic Acid
Authors: Kinoshita Mitsuhiro , Nakada Saburo , Umezawa Sumio 
Published: July 2006

Abstract
In continuing our study of the relationship between structural and antitumor activity, α-acetylamino acids containing a terminal methyleneketo group (namely, 2-acetamido-5-oxo-6-heptenoic acid, and 2-acetamido-4-oxo-5-hexenoic acid) and related derivatives have been synthesized. Their structures were confirmed by a study of their chemical reactions and their ultraviolet and infrared absorption spectra. It has been found that methyl esters of the α-acetylamino acids showed significant antitumor activity, whereas the free N-acetyl acid failed to show such activity.