bluuebunny/crossref_metadata_2025 huggingface dataset:
Separation Factors of Adjacent Rare Earths between the Aqueous and Resin Phases in the Presence of EDTA
Authors: Noguchi Masaru , Yoshifuji Akashi , Hagiwara Zenzi
Published: July 2006

In order to find the accurate separation factors of two adjacent rare earths between the aqueous and resin phases, measurements were performed at 30°C in the presence of EDTA and using Dowex 50W, X-8, 50–100 mesh. The following results were obtained under the same experimental conditions as were employed in ion-exchange system for the isolation of the rare earth series. The separation factors were 2.05 for Er-Tm, 1.88 for Dy-Ho, 1.61 for Y-Dy, 1.76 for Tb-Y, 1.30 for Eu-Gd, and 3.77 for Sm-Nd. In the Er-Tm separation factor, a fairly large discrepancy was observed between the calculated and experimental values. It is concluded from the experimental results that the separation factors of pairs of lanthanons should be directly measured.
Electrochemical Behavior of Platinum in Solutions Containing Ethylenediaminetetraacetate
Authors: Tanaka Nobuyuki , Fujisawa Tadashi
Published: July 2006

The electrochemical behavior of platinum in solutions of ethylenediaminetetraacetate(EDTA) has been investigated by the measurements of current-potential and current-time curves and by the controlled-potential electrolysis. EDTA gives the anodic limiting current, which is much smaller than that of one-electron transfer obtained for the ordinary diffusion-controlled electrode reaction. Platinum was detected by the spectrophotometric method in the solution which was subjected to the electrolysis at controlled potential. The results suggest that the anodic current is due to the electrolytic dissolution of the platinum electrode by the reactions,

Pt+2H2O→Pt(OH)2+2H+2e (1)

Pt(OH)2+H2Y2−→PtY2−+2H2O (2)

where Y4− represents a quadrivalent anion of EDTA.
An Automatic Chromatographic Method for the Separation of Flavonoid Compounds
Authors: Hori Masatake
Published: July 2006

A new chromatographic method for the separation of flavonoids was developed using Amberlite XAD-2 adsorption resin as the stationary phase and a gradient system of ethanolwater as the eluent. The advantage of the method lies in the fact that a number of flavonoids can be separated by a single operation with good reproducibility. The accuracy of this method determined with pure flavonoids was within ±2%. In addition, the method is useful for preparative purposes, because the solvents used are readily removable by evaporation. The elution time of 56 flavonoids was determined by this method; moreover, the method was applied to the determination of flavonoids in crude methanol extracts from plants (Scutellaria baicalenisis, Citrus aurantium and Crataegus cuneata).
Anionic Telomerizations of Styrene with Some Secondary Amines
Authors: Asahara Teruzo , Sen\={o} Manabu , Tanaka Sadayoshi , Den Norio
Published: July 2006

The anionic telomerizations of styrene with some secondary amines catalyzed by sodium metal were investigated. In this reaction a secondary amine was used as a telogen and styrene as a taxogen. Three telomers, i. e. N,N-disubstituted 2-phenylethylamine, N,N-disubstituted 2,4-diphenylbutylamine and N,N-disubstituted 2,4,6-triphenylhexylamine were separated from the mixture of the produced telomers under vacuum distillation. Proton NMR spectra of these telomers in carbon tetrachloride were consistent with the expected structural formulas. The reaction scheme was proposed to explain the formation of telomers.
The Autoxidation of Ethylbenzene in the Presence of the Aqueous Phase
Authors: Hotta Hiroshi , Ito Masayuki , Murashima Hiroaki
Published: July 2006

Ethylbenzene was oxidized to acetophenone and a small amount of benzaldehyde in the presence of the aqueous phase under oxygen pressure at 190°C. The yield of acetophenone decreased in the presence of sulfuric acid, sodium sulfate, and iron and copper sulfates. The formation of benzaldehyde was promoted in the presence of iron and copper sulfates and sulfuric acid. These effects can be explained mainly by the decomposition of α-phenylethyl hydroperoxide by the solutes in the aqueous phase.
Electrolytic Polymerization of Acrylonitrile. Kinetic Approach and Effect of Supporting Electrolytes
Authors: Asahara Teruzo , Sen\={o} Manabu , Tsuchiya Mitsuru
Published: July 2006

The electrolytic polymerization of acrylonitrile in constant current was examined by using several supporting electrolytes and the reaction mechanism was discussed. An explanation was given for the anomaly characteristic of the cathodic polymerization using sodium nitrate as a supporting electrolyte, which was reported by Funt. It was revealed that the polymerization is initiated by a radical mechanism at the anode and by an anionic mechanism at the cathode. The termination reaction of the anionic polymerization was analyzed by a kinetic approach and from the structural information of polymers obtained.
Studies of Ion Exchange Membranes. XXX. The Tetrahydrofuran Extraction of the Ion-exchange Membrane and Its Base Membrane Prepared by the “Paste Method”
Authors: Mizutani Yukio
Published: July 2006

In order to throw light on the chemical structure of the ion-exchange membrane prepared by the “Paste Method,” the ion-exchange membrane and its base membrane were extracted with tetrahydrofuran. The base membrane was composed of polyvinyl chloride and the resin component of the styrene-divinyl benzene system or of the 2-methyl-5-vinyl pyridine-divinyl benzene system, the ion-exchange group was introduced into this resin component. It was established that the resin component was partially extractable through a filter paper. Although the resin component and polyvinyl chloride should be entwined with each other, and although the resin component might be grafted on polyvinyl chloride, it could be concluded that the chemical structure of the ion-exchange membrane prepared by the “Paste Method” is different from that of Amberlite IR-120, i. e., the homogeneously crosslinked gel-structure.
Adsorption of Surface Active Substance at Aqueous Surface Using Tritium Labeled Compounds: Adsorption from Mixed Aqueous Solution of Sodium Dodecylsulfate and Dodecanol
Authors: Tajima Kazuo , Muramatsu Mitsuo , Sasaki Tsunetaka
Published: July 2006

Adsorbed amount of sodium dodecylsulfate (SDS) and n-dodecanol (DOH) at the gas-solution interface of their mixed aqueous solution was directly measured as a function of bulk concentration of DOH by the radiotracer method. For this purpose the surface radioactivity of the mixed solution in which either SDS or DOH was labeled with tritium, was counted by using a 2π window-less gas-flow counter. It was found that the adsorbed amount of DOH rapidly increases with increasing bulk concentration of DOH, while that of SDS gradually decreases. The adsorption of DOH and desorption of SDS are not a simple 1 : 1 replacement. A maximum total adsorption of about 13×10−10 mol/cm2, which exceeds the amount of close-packed monolayer adsorption extends over a wide range of concentration studied. It was suggested that the adsorbed film consists of mixed monolayer or double layers. The latter film is composed of mixed monolyaer of SDS and DOH with adsorbed layer of SDS beneath. The molar ratio of adsorbed amount of DOH to SDS in the surface became unity, when the ratio of the bulk concentration of DOH to SDS was about one hundredth, which shows a stronger adsorption tendency of DOH than that of SDS.
The Crystal and Molecular Structure of the High-melting-point Isomer of Bis-(1,2-diethoxycarbonyl-ethyl)tin Dibromide
Authors: Kimura Toshihide , Ueki Tatzuo , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The high-mp isomer crystal of bis-(1,2-diethoxycarbonyl-ethyl)tin dibromide (mp 122–123°C) is monoclinic: a=19.46, b=10.25, c=13.20 Å, β=121.1°; space group C2⁄c; four molecules are contained in a unit cell. The molecule has the C2 symmetry. The tin atom lies on the two-fold axis, and the coordination about the tin atom is nearly octahedral. Similar to the low-mp isomer, two bromine atoms attached to the tin atom are in cis-positions; also, two ligands, both 1,2-diethoxy-carbonyl-ethyl groups, are bound to the tin atom by oxygen and carbon atoms, forming rather puckered five-membered rings. Both rings are in either the d- or l-form, instead of consisting of one d- and one l-form, as in the low-mp isomer.
Effects of Metallic Surfaces on the Thermal Decomposition of Ethane
Authors: Nishiyama Yoshiyuki
Published: July 2006

The thermal decomposition of ethane was conducted in a static system at 700°C, using a silica vessel packed with a sheet of metal. Various sorts of metals were tested. The rate of ethylene formation decreased notably in the presence of metals as compared with the rate in an unpacked vessel, the decrease being larger at lower pressures. The activity of metals to reduce the rate was in order: Zr>Ti>Fe>Cu>W,Ag>Pt,Mo. The rate of methane formation did not change with the packing of metals. The main reactions were assumed to be radical reactions in the gas phase. From the observed order of reaction, it was concluded that the action of metal is to catalyze the recombination of hydrogen atoms and therefore to terminate the radical-chain reactions. A similar action was noted in hydrogen dissolved in a titanium sheet.
Measurement of Negative Ions Formed by Electron Impact. IV. Negative Ion Mass Spectra and Ionization Efficiency Curves of Negative Ions of m/e 17 and 16 from n-Propyl and Isopropyl Alcohols
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro
Published: July 2006

The negative ion mass spectra of n- and iso-propyl alcohols, with emphasis on their relative yields to the positive ions under 80 eV, 40 eV and 15 eV electron energies, and the ionization efficiency (IE) curves of OH− and O− ions to the extent of 50 eV electron energies were measured. In both cases, the electron impacts of 80 eV and 40 eV gave almost the same negative ion mass spectra, in which the relatively strong peaks of m⁄e 16 (O−), m⁄e 17 (OH−) and m⁄e 25 (C2H−) ions except for the decrement of C2H− ions in 40 eV for isopropyl alcohol were characteristic. For n-propyl alcohol, the ratio of the yield of CH2OH+ ions to that of O− ions (CH2OH+/O−) gave the values of 6.9×104 and 1.9×105 in 80 eV and 40 eV. For isopropyl alcohol the values of C2H4OH+/OH− were 3.3×104 and 6.4×104 in 80 eV and 40 eV, respectively. The comparison of the yield of negative ion in 10 eV with that of positive ion in 15 eV gave CH2OH+/O−=2.0×104 and C2H4OH+/OH−=2.3×103. Each appearance potential observed in IE curves is well interpreted by the following reactions. [OH− ions], for the first process C3H7OH(n- or iso-)+ e−→OH−+ C2H4+CH2+H, for the second process C3H7OH(n- or iso-)+ e−→OH−+CH3+CH2+CH2++e− or OH−+C2H4+CH2+H+e−. [O− ions], for the first process C3H7OH(n- or iso-)+e−→O−+C2H5+CH3, for the second process C3H7OH(n- or iso-)+e−→O−+C2H4+CH3+H or O−+C2H3+CH3+H2 and for the third process C3H7OH(n- or iso-)+ e−→O−+C3H7(n-or iso)+H++e− or O−+C3H5+H2+H++e−.
Reactions of Thiamine Disulfide Monosulfoxides with Mercaptans
Authors: Tsukamoto Goro , Watanabe Toshio , Utsumi Isamu
Published: July 2006

It was found that the reaction of thiamine disulfide monosulfoxide (I) with mercaptan is a competitive reaction between the so-called mercaptan-thiolsulfinate reaction and the apparent oxidation reduction reaction. This reaction offers an excellent method for the preparation of the mixed disulfides of thiamine and t-mercaptan or the unstable mixed disulfides, such as thiamineglutathione disulfides.
Alkoxysilanes. III. Preparation of Alkoxysiloxyaminosilane and Some of Its Reactions
Authors: Abe Yoshimoto , Kijima Ichiro
Published: July 2006

Bis(tri-t-butoxysiloxy)diaminosilane was prepared by the reaction of the corresponding di-chlorosilane with ammonia. It was also obtained by the reaction of silicon tetrachloride with tri-t-butoxysilanol in the presence of pyridine as a dehydrochloric acid agent, followed by the subsequent reaction of the mixture with ammonia. The alcoholysis, transamination reaction, hydrolysis, and acetolysis of this compound with n-butyl alcohol, phenol, aniline, n-butylamine, water, and acetic acid led to the formation of the corresponding bis(tri-t-butoxysiloxy)silane derivatives. In these reactions, the measurement of the ammonia evolved made it possible examine the relative reactivity of the reactants. An attempt to isolate the triaminosilane by the reaction of tri-t-butoxysiloxytri-chlorosilane with ammonia resulted in the formation of tetraaminocyclotetrasilazane and a polymeric substance containing the silicon-nitrogen bond.
Kinetic Features of the Redox-polymerization of Acrolein with the Potassium Persulfate-Silver Nitrate System
Authors: Kagiya Tsutomu , Morita Shigeru , Fukui Kenichi
Published: July 2006

The polymerization of acrolein initiated by the potassium persulfate-silver nitrate redox system in water was studied at 0°C from the point of view of kinetics. The potassium persulfate concentration was varied over the range from 15.75 to 157.5 mmol/l, and that of the initial monomer, from 0.462 to 2.675 mol/l, while the concentration of silver nitrate was 31.5 mmol/l. Both the polymerization rate and the molecular weight of the polymer were found to increase with the reaction time in the early stage, while in the stage of higher conversion the polymerization rate was gradually reduced and the molecular weight remained constant. In the early stage of the polymerization, the polymer yield showed a first-order dependence on the potassium persulfate and initial monomer concentrations. The molecular weight of the polymer was proportional to the monomer concentration, independent of the catalyst concentration. From these results, the kinetic features were discussed.
Graphical Evaluation of the Rate Constants of the Elementary Reactions in the Acrolein Polymerization with the Potassium Persulfate-Silver Nitrate Redox System
Authors: Kagiya Tsutomu , Morita Shigeru , Fukui Kenichi
Published: July 2006

A quantitative study was made of the redox-polymerization of acrolein initiated by the potassium persulfate-silver nitrate system. The reaction mechanism of this polymerization was proposed on the basis of the results of the time-conversion, time-molecular weight curves, and also on the basis of the characteristic features of this polymerization, reported in a previous paper. The rate constants of the elementary reactions in this polymerization were estimated by a graphical method. In the early stage, neither the termination nor the transfer reaction is very remarkable as the initiation reaction, but in the later stage the termination reaction by a recombination of the polymer radical and the transfer reaction increase with the reaction time, as does the initiation reaction also.
Catalytic Activities of Salicylaldehyde Derivatives. I. Catalytic Effects of 4-Formyl-3-hydroxyphenyltrimethylammonium Bromide on the Racemization of l-Amino Acid
Authors: Ando Makoto , Emoto Sakae
Published: July 2006

The pyridoxal-like catalytic effects of salicylaldehyde derivatives on the racemization of amino acid in the presence of a metal ion is known to be promoted by the substitution of an electron-attracting group in the benzene ring. Of the salicylaldehyde derivatives tested thus far, 4-formyl-3-hydroxyphenyltrimethylammonium bromide shows the most effective catalytic activity of racemization at pH 10 and at 80°C; the rate constant was 11.0×10−3 min−1. The catalytic activity of this compound was studied under various conditions; the activation energy of the racemization of l-glutamic acid at pH 10 was 14.3 kcal/mol.
Catalytic Activities of Salicylaldehyde Derivatives. II. Kinetic Studies of the Racemization of Amino Acid
Authors: Ando Makoto , Emoto Sakae
Published: July 2006

In the racemization reaction of l-glutamic acid, catalyzed by salicylaldehyde derivatives and cupric ions, the rate constants, k, of 3-bromo-, 3-methoxy-, 3-methyl-, 3-nitro-, 4-methyl-, 5-bromo-, 5-methoxy-, 5-methyl-, and 5-nitro-salicylaldehydes and of salicylaldehyde were measured and the kinetic relation between the rate constant, k, of the salicylaldehyde derivatives and the corresponding Hammetfs constant, σ, was studied. A linear relation between logk and the σ of 4- or 5-substituted salicylaldehydes and another linear relation between logk and the σ of 3-substituted salicylaldehydes were found. The activation energies of the racemizations catalyzed by pyridoxal, 3-nitro-, and 5-nitro-salicylaldehydes and by salicylaldehyde were determined, but no distinct difference between 3-nitrosalicylaldehyde and 5-nitrosalicylaldehyde was observed.
Conformational Studies of Acetonated α-l-Sorbo- and β-d-Fructopyranoses by Means of Proton Magnetic Resonance Spectroscopy
Authors: Maeda Takashi , Tori Kazuo , Satoh Shiroh , Tokuyama Kanji
Published: July 2006

The favored conformations of the pyranose rings of several acetonated α-l-sorbo- and β-d-fructopyranoses have been revealed by proton magnetic resonance spectroscopy. The conformations of the rings of the pyranoses are unchanged by the introduction of 1,2-O- or 1,3-O-isopropylidene groups in α-orientation of l-sorbose, but they are affected by the introduction of the 2,3-O-isopropylidene group. These findings support the fact that 2,3-O-isopropylidene-α-l-sorbopyranose was not obtained by the acetonation of l-sorbose. The rings of diacetonated d-fructopyranoses with a cis-fused acetal ring adopt a distorted conformation; however, those of diacetonated l-sorbopyranoses with a trans-fused acetal ring are only slightly distorted from the stable 1C conformation. Angyal’s anticipation of the difficult acetalation of the trans-glycol of a pyranose has been further experimentally supported.
The Acetalation Mechanism of l-Sorbose
Authors: Maeda Takashi , Miichi Yoshiyuki , Tokuyama Kanji
Published: July 2006

The following reaction mechanism of the acetonation of l-sorbose is proposed:

(Remark: Graphics omitted.)

2,3:4,6-di-O-acetal (furanose) (II). The pyranose-to-furanose ring conversion (I→II) proceeds via the keto-form intermediates Vk and VIk; VIk is formed by the preferable attack of acetonating reagents on the primary hydroxyl group at the C6 of Vk followed by cyclization with the hydroxyl group at C4. The isolation of such keto-form intermediates as were successfully obtained from the acetalations of 1-O-methyl- (X) and 1,6-di-O-methyl-l-sorboses (XVIII) gave strong support to the above mechanism. This acetonation mechanism can also be used in the other acetalations of I; however, in the case of the benzylidenation there is a possibility that the reaction might be via the pathway of 1,3-O-acetal (pyranose)\ightleftarrows1,3-O-acetal (furanose) (Vb)→1,3: 4,6-di-O-acetal (furanose).
A Destructive Ethylation Reaction of Benzene with 3-Methylpentane-1-14C
Authors: Sugahara Yukio , Hayami Jun-ichi , Sera Akira , Goto Ryozo
Published: July 2006

The destructive alkylation reaction of benzene with 3-methylpentane to give ethylbenzene in the presence of aluminum chloride was investigated. When 3-methylpentane-1-14C was employed, radioactive ethylbenzene was obtained. A radioassay of radioactive ethylbenzene showed that: a) the specific radioactivity of the ethylbenzene was about one-third that of the starting 3-methylpentane-1-14C, and b) more than 90% of the radioactivity of the ethylbenzene was present on the β-carbon atom of the ethyl group. These findings suggested a preceding equilibrium between 3-methylpentane and 2-methylpentane, which resulted in an equivalent localization of the radioactive label on three methyl groups of these C6-hydrocarbons. A carbonium-ion mechanism including an intermediate ethyl cation was discussed in detail.
Synthesis of 2-Amino-4-hydroxy-6-acetyl-7-methyl-7,8-dihydropteridine
Authors: Sugiura Katsura , Goto Miki
Published: July 2006

2-Amino-4-hydroxy-6-acetyl-7-methylpteridine was synthesized by condensation of 2,4,5-triamino-6-hydroxypyrimidine and triketopentane. Reduction of this compound with sodium amalgam yielded a coloring matter, whose UV-spectra and chemical reactions strictly correspond to those of sepiapterin or isosepiapterin. On the basis of NMR spectra, the coloring matter was proved to be 7,8-dihydro-2-amino-4-hydroxy-6-acetyl-7-methylpteridine. Hence, it can be concluded that sepiapterin has the 7,8-dihydro structure as proposed by Nawa.
Partial Asymmetric Synthesis in the Simmons-Smith Reaction. III. A Modification of the Reaction
Authors: Sawada Seiji , Inouye Yuzo
Published: July 2006

A modification of the Simmons-Smith reaction, which involves a prior reaction of ethyl iodide with zinc copper couple followed by addition of methylene iodide and oleflns, was proposed. The improved yields of cyclopropane products were obtained with various olefin substrates. It is likely that the operating species in the present modification is ethyliodomethylzinc.
The Rate of Penetration of Photographic Chemicals into Gelatin Layers. I. Diffusion Rate of Developing Materials
Authors: Iwano Haruhiko
Published: July 2006

The rate of diffusion of various kinds of developing materials through coated gelatin layers was determined by using silver halide as a detector. p-Phenylenediamines have the biggest diffusion constants among materials tested. They have no pH-dependency nor concentration-dependency. p-Aminophenols have slightly lower diffusion constants than the corresponding p-phenylenediamines. The constants increase with increase in molecular sizes and also with pH. Hydroquinones have relatively low diffusion constants. They are considerably affected by variation of pH, concentration and ionic strength. These characteristics are discussed in connection with the chemical structures of developing materials.
Hybridization of Carbon and Equilibrium Distance
Authors: Miyazaki Tomoo , Ohbayashi Hidehito
Published: July 2006

The CNDO/2 method, an approximate self-consistent molecular orbital theory, has been applied to the calculation of equilibrium distances of the carbon-hydrogen bond and the normal and hypothetical carbon-carbon single or double bonds which are usually considered te-te, tri-tri, di-di and te-tri single bonds or tri-tri and di-di double bonds between carbon hybrids. The electronic interaction energies between non-adjacent atomic orbitals for sigma system considering appropriate carbon hybrids have been estimated. From the results of these calculations, it follows that the carbon-carbon bond length of sigma system is little affected by the types of hydbridization of carbon atoms.
Studies of the Direct Dissolution of Metal in a β-Diketone Reagent
Authors: Sato Kimitaka , Kammori Ohiko
Published: July 2006

As it was found that metallic iron is dissolved in acetylacetone (Hacac), the interaction between the solute and the solvent in the dissolution phenomena, together with the process of the dissolution of metal, were examined in detail in order to apply it to analytical techniques. The factors of the oxygen, the co-existing water, and the dissociated proton in acetylacetone were shown to be effective in the dissolution. With typical β-diketones, the exception of acetylacetone, such as trifluoroacetylacetone (HTFA), hexafluoroacetylacetone (HHFA), benzoyltrifluoroacetone (HBTA), 2-furoyltrinuoroacetone (HFTA), and 2-thenoyltrifluoroacetone (HTTA), were also employed; they were shown to have the same properties as the above one. The relationship between the solubilities of metals and the effect of adding an organic solvent, the equilibrium reactions of fluorine-containing β-diketones with water or alcohols, or the preferred enol forms of trifluorosubstituted β-diketones, were also discussed, paying attention to the accelerating effects of the solvents on the dissolution.
Effects of Cation Vacancies of the Diffusion of Nickel Ions in Defective Spinels
Authors: Yamaguchi Goro , Nakano Mitsuko , Tosaki Mamoru
Published: July 2006

In order to clarify the influence of composition-dependent cation vacancies in defective spinels on the diffusion, the diffusion rates of Ni2+ in several kinds of defective spinels (MgO·xAl2O3, where x=1.1,1.2,1.3,1.4 and 1.5) and a perfect spinel (MgO·Al2O3) were measured by the use of an electron probe micro-analyzer, and the diffusion coefficients were obtained. The diffusion coefficients were found to be linear to the concentrations of the composition-dependent vacancies. The so-called activation energies which were calculated from the Arrhenius plot were about 70 kcal/mol for the defective spinels and 106 kcal/mol for the perfect spinel. It may be concluded that composition-dependent cation vacancies govern the diffusion of cations in the defective spinel, while temperature-dependent vacancies probably predominate in the perfect spinel.
The Chromium(III) Complexes with β-Aminoethylsulfonic-N,N-diacetic Acid and Aspartic-N,N-diacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following chromium (III) complexes with the β-aminoethylsulfonic-N,N-diacetic acid (AEDA) and aspartic-N,N-diacetic acid (ASDA) were newly prepared; K3[Cr(aeda)2]·4H2O (pale red) (I), [Cr(OH)(Haeda)(o-phen)]·2H2O (orange) (II) and [Cr(Hasda)(H2O)2]·H2O (reddish purple) (III). From the results of spectral measurments, it was found that AEDA acts as a quadridentate ligand as well as a terdentate one in an aqueous solution, but only as a terdentate ligand in a crystal state, and that the coordinating ability of the oxygen atom of sulfonic radical in AEDA is weaker than that of carboxylic radical in ammoniapropionicdiacetic acid (APDA). In Complex III, ASDA behaved as a quadridentate ligand rather than as a quinquedentate. Complexes II and III showed some interesting thermal decomposition processes. The former lost one mole of water at 110°C from the hydrogen atom in free sulfonic acid radical and the coordinated OH group, accompanied with the increase of coordination number of AEDA from 3 to 4. In the latter, one mole of crystalline water was lost first, and then the carboxylic acid bound to the methylene group at β-position in the ligand was decomposed to liberate carbon dioxide, and the coordinated asda was changed into apda.
The Kinetics of the Ligand-substitution Reactions of Nitrilo(diacetic)-propionato- and Nitrilo(diacetic)isopropionatoniccolate(II) Ions with EDTA, and of Taurin-N-diacetatoniccolate(II) Ions with EDTA and CyDTA
Authors: Kimura Masaru
Published: July 2006

The kinetics of the reactions of nickel(II)-nitrilo(diacetic)propionate (NDAP) and nickel(II)-nitrilo(diacetic)isopropionate (NDAIP) complexes with ethylenediaminetetraacetate (EDTA) ions, and those of the nickel (II)-taurin-N-diacetate (TDA) complex with EDTA and trans-1,2-cyclohexanediaminetetraacetate (CyDTA) ions, have been studied polarographically in solutions with pH 4.8–6.0 at 25°C and at an ionic strength of 0.2. All the reactions except those with CyDTA proceeded through four reaction paths, and the rate constants for the reaction paths were determined. The reaction of the nickel(II)-TDA complex with CyDTA was found to proceed only through the complete dissociation of the Ni(II)-TDA complex. There was not a direct reaction of the complex with CyDTA. Consequently, the overall reaction with CyDTA became much slower than that of the same complex with EDTA. The rate constants obtained were compared with those of the similar reactions of the nickel (II)-nitrilotriacetate (NTA) complex with EDTA and CyTDA which had been reported previously. The rate of the dissociation reaction of nickel(II) complexes increased in the order: NDAIP≤NDAP<NTA<TDA. Especially, the rate of the Ni(II)-TDA complex was about 30 times that of Ni(II)-NTA complex.
Shock Induced Reactions of Methane with Nitrous and Nitric Oxides
Authors: Drummond L J
Published: July 2006

Reflected shock waves, generated in a 5×3 inch shock tube, have been used to ignite mixtures of methane-nitrous oxide and methane-nitric oxide. Monochromators, a pressure transducer and an oscilloscope were used to determine the induction period to ignition (τ) after the reflected wave passed the window. A flash lamp and spectrograph were also used to obtain spectra before and after explosion. For CH4-N2O mixtures it was found that the plot of log(τ[N2O]p5) against inverse temperature was linear and the activation energy was about 60 kcal/mol. This indicates that the rate controlling process was the reaction N2O(+M)→N2+O(+M). However, the reaction CH3+N2O→CH2+N2+OH may also be important. The results for CH4-NO mixtures could be expressed by log(τ[NO]p5)=−10.2+49000⁄4.58T which suggests to the reaction CH2+NO→CH+HNO may be rate controlling. Spectrographic plates showed that CN and OH were present during the induction period but only OH was detected after explosion. This indicates that the reactions CH+NO→CN+OH and CN+NO→N2+CO may be a significant mechanism for achieving the reduction of nitric oxide.
Thermal Decomposion Reactions of Chromium(III) Complexes. Hexammine, Chloropentammine and cis-Dichlorotetrammine Complexes
Authors: Tanaka Nobuyuki , Nagase Kenzo
Published: July 2006

The thermal decomposition reactions of [Cr(NH3)6]Cl3, [CrCl(NH3)5]Cl2 and cis-[CrCl2-(NH3)4]Cl in solid state were studied by the manometric, infrared spectroscopic and reflectance spectroscopic methods. The decomposition of these complexes in vacuum was initiated by substitution of an outer-sphere chloride ion for a coordinated ammonia. The rate constants, activation energies and activation entropies of these substitution reactions were obtained and the possible reaction processes were discussed. The products cis,cis-[CrCl3(NH3)3] and cis,trans-[CrCl3(NH3)3] were obtained on the heating of cis-[CrCl2(NH3)4]Cl.
Reaction of Titanium Tetrahalides with Phenylhydrazones
Authors: Aggarwal R C , Singh S K
Published: July 2006

Titanium tetrafluoride reacts with benzaldehyde phenylhydrazone to yield 1:1 adduct and with benzophenone phenylhydrazone 1:2 as well as 2:1 adducts, while other tetrahalides form 1:1 adducts with both the phenylhydrazones. All these complexes are coloured and stable at room temperature. The infrared spectral studies of phenylhydrazones and their titanium (IV) complexes have been made in the 4000–200 cm−1 region.
Configuration of 1,3-Dipolar Cycloaddition Products of Nitrones with N-Phenylmaleimide
Authors: Iwakura Yoshio , Uno Keikichi , Hongu Tatsuhiko
Published: July 2006

1,3-Dipolar cycloaddition reaction of aldonitrones such as C-2-furyl-N-phenyl-, C,N-diphenyl-, and C-2-thienyl-N-phenylnitrone with N-phenylmaleimide was carried out. The product was separated into two stereo isomers, cis and trans isoxazolidines with respect to H3 and H4, which were identified by NMR spectra. Spin-spin coupling of protons on C3 and C4 of isoxazolidine ring was found to be 8.4–9.0 cps for cis isomers and to be zero for trans isomers.
Effect of Ultrasonic Waves on Eriochrome Black T
Authors: Prakash Sheo , Jain S K
Published: July 2006

Ultrasonic waves of high frequency (1 Mc/sec) have been employed to study the effects on the dilute aqueous solution of Eriochrome Black T. The deaeration of the solution by nitrogen does not greatly affect the rate of decolourization. The process is irreversible and the kinetic study shows it to be unimolecular. Oxidation and subsequent destruction of the dye molecule has been found to be the cause of the fading of the dye solution.
Alkaline Hydrolysis of Aryl Benzenethiolsulfinates
Authors: Oae Shigeru , Yoshikawa Yoichiro , Tagaki Waichiro
Published: July 2006

The alkaline hydrolysis of substituted phenyl benzenethiolsulfinates has been kinetically investigated. The rates were correlated with the second order kinetic equation, first order with respect to each of the hydroxide and the ester concentration. The second order rate constant for the unsubstituted ester was found to be 3.17×103  l/mol sec (water, 30°C). The Hammett ρ values were found to be ρX,Y=H=2.4 and ρY,X=H=1.6 for (Remark: Graphics omitted.) respectively.
Effect of Cationic Detergents on the Lecithin Stabilized O/W Emulsion
Authors: Sastry T G , Srivastava S N
Published: July 2006

An oil-in-water system (Nujol being the oil phase) stabilized by the phospholipid, lecithin, has been chosen in this study. The system being negatively charged initially, cationic detergents like lauryl pyridinium chloride (LPC), Cetyl pyridinium bromide (CPB), Phenyl trimethyl ammonium chloride (Ammonyx-200) and Cetyl dimethyl benzyl ammonium chloride (CDBAC) have been employed in order to study their influence on the flocculation and coalescence rates and the degree of aggregation haemocytometrically. Zeta potentials (ξ) have been determined at the corresponding concentrations of the detergents by microcataphoresis and with these values the potential energies and then ultimately the operating van der Waals constant of the system has been determined. From the log C-ξ values it is evident that except Ammonyx-200 which is not an effective cationic detergent, all the others have reversed the charge of the system and their efficiencies are in the order CDBAC>CPB>LPC. The different binding parameters, number of binding sites available for adsorption and free energy of the surface have also been calculated.
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

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

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

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

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−<Br−<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

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

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

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

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

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

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

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

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

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

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

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

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

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>CuCl>>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>ZnCl2>AgCl>>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.