bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of Sulfosodalite, an Ultramarine-Relating Phase
Authors: Yamaguchi Goro , Kubo Yasushi
Published: July 2006

A sulfur-containing sodalite-type aluminosilicate, 6NaAlSiO4·Na2S (designated sulfosodalite in this paper), was synthesized in the system NaAlSiO4-Na2S at temperatures 850 to 950°C in an H2 or N2 atmosphere. All of the sulfur in this substance was contained as sulfide ion S2−, and its equilibrium content in a unit cell increases with temperature from 1.5 S at 850°C to 1.8 S at 950°C. This substance was only pale colored, yellowish or pinkish, but the partial substitution of Si for Al produced a deep vermilion red color.
The Isokinetic Temperature of the Acylation of l-Menthol
Authors: Akiyama Fuminori , Tokura Niichiro
Published: July 2006

The acylations of l-menthol with p-substituted benzoyl- and substituted acetyl chlorides were carried out, and it was found that the electron-releasing substituents accelerate the reaction rate in chloroform even though the reaction is completely of the SN2 type. This result is interpreted in relation to the low isokinetic temperature, the reaction itself being carried out above that temperature. Such a phenomenon is discussed in terms of the configurational and the solvent effects on the entropy of activation.
Relative Determination of Soret Coefficients of Alkaline Earth Chlorides
Authors: Ikeda Toshio , Ohe Hidefusa , Kawamura Saburo
Published: July 2006

The Soret coefficients of aqueous solution of alkaline earth chlorides were determined indirectly using combined thermocells. “Combined thermocell” refers to a cell system of a back to back combination of two thermocells made of common electrodes and different electrolytes without liquid junction. The values are −2.79 for MgCl2, −3.43 for CaCl2, −4.09 for SrCl2, and −4.73 for BaCl2, respectively (in the unit of 10−3 deg−1) at 0.005 m and 25°C. These agree with reported values found by the direct method.
Radiolysis of Hydrogen Cyanide in an Aqueous System. II. Effects of Additives and Reaction Mechanism
Authors: Ogura Hajime
Published: July 2006

The 60Co γ-irradiation of dilute aqueous solutions of hydrogen cyanide (6 mm) in the absence of oxygen yielded mainly ammonia with G=1.9, formaldehyde with G=1.1, and carbon dioxide with G=0.8, while G(–HCN)=5.8 molecules per 100 eV. Polymeric hydrogen cyanide was also observed with the G(–HCN(polymer))\simeq4, which showed an intense broad absorption band in the UV region upon γ-irradiation. The following material balances were observed with the main products:

G(-HCN)\simeqG(NH_3)+G(-HCN(polymer))\simeqG(CO_2)+G(HCHO)+G(-HCN(polymer))

The results can be interpreted in terms of a mechanism involving HCN−, H2CN, and H(OH)CN radicals. The ratio of the rate constants for the reactions of e−aq and H atoms with hydrogen cyanide to those with several scavengers have been determined as k(e−aq + HCN)/k(e−aq + NO3−)=0.019 and k(H + HCN)/k(H + 2-propanol)=1.4, all at 17°C.
Phase Transitions in Crystalline Divalent Metal Dicalcium Propionates. II. Proton Magnetic Resonance Investigation
Authors: Nakamura Nobuo , Suga Hiroshi , Chihara Hideaki , Seki Syûzô
Published: July 2006

The motions of the propionate anions in strontium-, lead-, and barium-dicalcium propionates were examined with the proton magnetic resonance method at low temperatures. It was found that the methyl groups rotate about the C3-axes even at 20°K in the Sr-, and the Ba-salts. In the Sr-salt the gradual decrease of the second moment below the ferroelectric transition point was observed and this phenomenon was related to the large angle torsional oscillations of the ethyl groups about the C3′-axes as introduced in Part I: Near the ferroelectric transition point the observed second moment shows the possibility of excitation of the C3′-rotation which would make the crystal to be paraelectric above the transition point. It was expected that the C3′-torsion is to some extent excited in the Pb-salt at liquid nitrogen temperature, a slight discrete change being observed at the lower transition point. A sharp line width transition was also observed in the Ba-salt and this fact resulted in the finding of a new λ-type phase transition with the peak at about 204°K by the differential thermal analysis. A slight decrease of the second moment was observed at the upper transition point and the C3′-rotation was assumed to be fully excited above that point.
Studies on the Sol-Gel Transformation of Aluminium Hydroxide in the Presence of Dyes
Authors: Malik Wahid U , Khan Iqbal A
Published: July 2006

The influence of dyes on the gelation of aluminium hydroxide sol has been studied with the help of viscometric and pH metric methods. From these studies it is inferred that the behaviour of acid dyes towards alumina is different from that of basic dyes. The results have been interpreted in terms of various structural changes taking place in the dye molecule. Adsorption studies reveal that the data do not fit well into the Langmuir or Freundlich adsorption isotherm equation in the case of alizarin sulphoric acid, while in the cases of methyl orange, methylene blue, and malachite green, the data are found to fit well into the Langmuir adsorption equation.
Kinetics of Isotopic Exchange between Acetylacetone-14C and Tris-acetylacetonatoaluminum in Tetrahydrofuran
Authors: Saito Kazuo , Masuda Kazuyo
Published: July 2006

Tris-acetylacetonatoaluminum [Al(acac)3] is precipitated crystalline from tetrahydrofuran (THF) solution containing an excess of acetylacetone (acacH) by adding chilled petroleum ether. This fact enables a kinetic study of isotopic exchange of acac− between [Al(acac)3] and acacH with the aid of acetylacetone-14C. The exchange rate is independent of the concentration of acacH and dependent on that of water. The rate formula at 25°C is as follows:

R=[Al(acac)_3](6×10^-5+2.0×10^-2[H_2O]) mol l^-1min^-1

This exchange reaction is catalysed by acids; the stronger the acid, the greater the catalytic effect. One of the acetylacetonate ligands would be present with one end free, and break of the remaining bond of unidentate acetylacetonate seems to be the rate determining step. Water can occupy the vacant coordination site of aluminum ion to retard recombination of the unidentate ligand. The donation of proton to the free end of acetylacetonate appears to impede the recombination, too, and facilitate the exchange. Hydronium ion seems to be the unique proton carrier.
Studies of Organic Catalytic Reactions. VI. The Function of Pyridine and Copper in the Rosenmund-von Braun Reaction
Authors: Ito Takehiko , Watanabe Ken-ichi
Published: July 2006

The Rosenmund-von Braun reaction with aryl halide, with its Ar-X+CuCN-Base→Ar-CN+CuX-Base, has been studied in nitrobenzene in place of an organic base at 160–180°C. The free nitriles formed during the reaction were determined exactly by gas chromatography. In the use of bases with suitable coordination forces to CuCN, the reactivity of the base for the substitution was found to be in the order: prim.>sec.>tert. A steric hindrance of the base was observed, and the reactivity of the pyridine homologue followed the order: pyridine>quinoline>α-picoline>2, 6-lutidine. Ortho-substituted groups in the halobenzene seem to manifest no steric hindrance on the reaction. From the results of the kinetic study, it can be said that CuCN participates in the reaction essentially in the form of a Base(1 mol)-CuCN complex. The overall reaction is second-order, dc⁄dt=k[Complex][Ar-X]. The rate-determining step may be in the halogen exchange stage in the intervening complex, Base-CuCN-Ar-X, where the plane including CN-Cu-X and that of the benzene ring may be nearly perpendicular to each other. When an excess of CuCN over the base is used, the base is liberated from the Base-CuX complex, after the displacement, and then coordinates to the unreacted CuCN again.
The Dimerization of Propylene over a Nickel Oxide-Silica-Alumina Catalyst
Authors: Imai Hisao , Hasegawa Touji , Uchida Hiroshi
Published: July 2006

The composition of hexene isomers produced by the dimerization of propylene over a nickel oxide-silica-alumina catalyst has been examined under the following experimental conditions: 10–300 kg/cm2, 100 and 200°C. Under a typical set of experimental condition (50 kg/cm2, 200°C), eight hexene isomers, i.e. 4-methyl-trans-2-pentene, 4-methyl-cis-2-pentene, 2-methyl-1-pentene, trans-2-hexene, cis-2-hexene, 3-methyl-trans-2-pentene, 3-methyl-cis-2-pentene, and 3-methyl-1-pentene, have been found to be the primary products of the dimerization. Among these, more trans isomers are produced initially than the corresponding cis isomers for 4-methyl-2-pentenes and 2-hexenes, but the reverse is true for 3-methyl-2-pentenes. Under higher pressures, 2,3-dimethylbutenes are also produced at 200°C. A reaction scheme assuming the intermediates of cyclobutane derivatives has been proposed to explain the above findings. The scheme may also explain the unique order of the activity of the present catalyst for a series of n-olefins.
Effect of Pressure on Graphitization of Carbon. I. Heat Treatment of Soft Carbon under 1,3 and 5 kbar
Authors: Noda Tokiti , Kamiya Kanichi , Inagaki Michio
Published: July 2006

Polyvinylchloride coke was heat-treated under the quasi-hydrostatic pressure of 1,3, and 5 kbar by using a simple piston cylinder type high pressure apparatus. The process of graphitization under pressure was studied kinetically by analyzing the profile of the (002) diffraction line. It was found that the accelerating effect of pressure on the graphitization of carbon became more pronounced at higher pressure. The process of graphitization under 3, and 5 kbar seemed to take place in at least two stages. In the first stage, the profile of the (002) line shifted simply from the position of the original line to 26.0° in 2θ, which corresponded to a c0-spacing of 6.85 Å. In the next stage, a new component, having a c0-spacing of about 6.72 Å, appeared in addition to the first component, having a c0-spacing of 6.85 Å. Therefore, the profiles of the (002) line became composite. Under 1 kbar, however, no composite profiles were observed and the c0 Spacing decreased gradually with heat treatment. Approximate values for the activation energy and activation volume for graphitization under 3–5 kbar were estimated to be 80–120 kcal/mol, and −7–−9 cc/mol, respectively.
High Pressure Copolymerization of Styrene and Vinyl Acetate with Vinyl Chloride
Authors: Imoto Tatsuya , Ogo Yoshiaki , Nakamoto Hideo
Published: July 2006

The radical copolymerization of vinyl chloride and styrene, and that of vinyl chloride and vinyl acetate, were investigated in an acetone solution at 50°C under high pressures of up to 3000 kg/cm2. The monomer reactivity ratios of these copolymers were not affected by the pressure, while their molecular weights and overall rates of copolymerization increased with the pressure. The increments of the four rate constants of the growing chain of copolymerization (k11,k12,k21, and k22) with the pressure are all of the same order. In such a case, ΔV*11 is ΔV*12, and ΔV*22 is ΔV*21 (ΔV*ij is the activation volume in which the i radical reacted with the j monomer). The conclusion drawn from our previous works, that the monomer reactivity ratios of the copolymerization between nonconjugated monomers are independent of the pressure was supported by the experimental results of this report.
The Photochemical Reduction of Hydrazobenzene
Authors: Hashimoto Shizunobu , Sunamoto Junzo , Nishitani Syunpei
Published: July 2006

Hydrazobenzene was irradiated with an ultraviolet light in n-hexane under a nitrogen atmosphere. The products were azobenzene, aniline, and a trace of semidines. The yield of azobenzene was usually larger than that calculated on the basis of the disproportionation of hydrazobenzene, while the yield of aniline was less. The reactions were followed by the determination of the disappearance of hydrazobenzene and that of the formation of azobenzene. On the basis of the available data, in the photochemical reaction of hydrazobenzene it was assumed that the formation of azobenzene was not due to the disproportionation, but to the oxidation of hydrazobenzene, and that no fission of the N–N bond of hydrazobenzene occurred to give azobenzene.
Kinetic Studies of the Oxidation of Benzils with Peroxyacetic Acid in Acetic Acid
Authors: Furuya Yoshiaki , Urasaki Iwao
Published: July 2006

The oxidation of benzils with peroxyacetic acid in the presence of sulfuric acid in acetic acid has been studied kinetically. The rate of the consumption of peroxyacetic acid has been found to be the sum of the four terms shown in the following equation:

-d[AcO_2H]/dt={k_d+k_t[H_2SO_4]}[AcO_2H]+{k_2+k_2’[H_2SO_4]}[Bz_2][AcO_2H]

It is considered that the first and second terms correspond to the decomposition of peroxyacetic acid itself and to the acid-catalyzed reversible transformation of peroxyacetic acid to acetyl peroxide, while the third and fourth terms represent, respectively, the non- and the acidcatalyzed oxidations of benzils with peroxyacetic acid. In both non- and acid-catalyzed oxidations, a probable mechanism passing through benzoic anhydride is postulated.
Syntheses and Reactions of Nitrogen- and Sulfur-Analogs of 2-Piperazinone
Authors: Masuzawa Kuniyoshi , Masaki Mitsuo , Ohta Masaki
Published: July 2006

2-Piperazinone oxime, 2-piperazinoneimine, and 2-piperazinethione were synthesized. The reaction mixture of ethylenediamine and glycolonitrile was treated with an excess amount of hydroxylamine in methanol to give 2-piperazinone oxime in a 53% yield. 2-Piperazinone oxime was easily reduced to 2-piperazinoneimine, which was then treated with hydrogen sulfide to yield 2-piperazinethione. Some reactions of these compounds are described.
Synthesis and Reactions of Functional Polymers. XXXIV. Low Polymerization of Ethylene Oxide with Sodium N,N-Dimethyldithiocarbamate in Dipolar Aprotic Solvents
Authors: Nakai Takeshi , Okawara Makoto
Published: July 2006

The low polymerization of ethylene oxide with sodium dimethyldithiocarbamate in a homogeneous system was studied. This reaction was verified as proceeding through a step-by-step addition mechanism, due to the enhanced nucleophilicity of the dithiocarbamate anion in dipolar aprotic solvents. The solvent effects and the catalyses of various dithiocarbamate salts were also examined. Epichlorohydrin was reacted with this salt in dimethylformamide to afford a polymer with a dithiocarbamate moiety through both ring-opening and substitution processes.
Solubility of Chlorine in Hydrochloric Acid
Authors: Hine Fumio , Inuta Shusei
Published: July 2006

The solubility of chlorine in a concentrated HCl solution at various conditions of concentration, partial pressure, and temperature was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3− was found to be proportional to the partial pressure of chlorine in the gas phase, and its slope was a function of the HCl concentration and the temperature Empirical equations representing these relations and the solubility of chlorine were obtained. It was confirmed that the results agreed with the experimental data in the 2–10 n HCl concentration range at partial pressures of chlorine lower than 1 atm and at 30–90°C. Such physico-chemical properties as the Gibbs free-energy change were considered by using the data of solubility, and the behavior of the system consisting of Cl−, Cl2, and Cl3− was discussed.
Initiation Step of Methane Pyrolysis
Authors: Yano Takayuki , Kuratani Kenji
Published: July 2006

Equimolar mixtures of CH4 and CD4 were pyrolyzed at 1560°K by a reflected shock wave. From the isotope distribution of H2, HD and D2 which are components of the product in early stage, the initiation step of methane pyrolysis is concluded to be the splitting to a methyl radical and a hydrogen atom.
Effects of Heating Temperature and Irradiation on the Catalytic Activities of Active Carbons for Phosgene Synthesis
Authors: Sato Shoichi , Yoneda Yukio
Published: July 2006

The kinetic factors for phosgene synthesis over thermal and irradiated sucrose carbons were examined in particular regard to their dependences on the heating temperature and irradiation. Gamma-irradiation on carbons prepared at 900 or 1000°C produced new active sites with EA of 11–12 kcal/mol. An explanation is suggested of the effects of heating temperature and irradiation on the catalysts; the catalytic activity is most reasonably related to the degree of growth of the network structure of carbons. In the case of carbons prepared by heating at 900 or 1000°C and having the structure grown to the largest extent, a high dose of gamma-rays presumedly destroys most efficiently the thermally generated active sites and forms sites with a high activation energy. Free radicals and peripheral atoms which also comprise characteristics of amorphous carbons seem to behave independently of catalytic activities and are supposed to have no direct relation to the activities.
Spectrophotometric Determination of Formation Constants of Iron(III) Complexes with Chloride Ion in Dimethyl Sulfoxide
Authors: Wada Goro
Published: July 2006

The formation constants of FeCl2+ and FeCl2+ have been measured in dimethyl sulfoxide (DMSO) containing Fe(ClO4)3, NaCl, HClO4 and NaClO4. Some spectrophotometric methods giving the formation constants and molar extinction coefficients of the complexes were developed and gave, on the average, logK1=3.62 and logK2=2.10, at 0.02 m HClO4 and an ionic strength of 0.10 m at 25°C. It is rather surprising that these values are only slightly larger than those in N-methylacetamide, which is expected, however, to give much smaller values than DMSO, due to its extraordinarily large dielectric constant. The species formed between Fe(III) and Cl− ion is reasonably supposed to be a true complex bonded directly with each other and not an ion-pair association product. At higher concentrations of Fe(III), formation of polynuclear complexes can occur.
Crystalline Complexes of Allylamine and Propylamine with Copper(I) Chloride and Bromide
Authors: Ogura Tetsuya , Hamachi Takeshi , Kawaguchi Shinichi
Published: July 2006

Crystalline 1 : 1 and 1 : 3 complexes of allylamine and propylamine with copper(I) chloride and bromide were synthesized in vacuo. Equilibrium vapor pressures of these complexes were measured at several temperatures and the enthalpy of ligation of each amine molecule was determined. Both the thermochemical and infrared absorption data indicate that in the 1 : 1 complexes of allylamine the ligand molecule serves as a bidentate, but in the 1 : 3 complexes the second and third ligand molecules link to the metal only through the amino nitrogen atom.
Reaction Rates in Binary Mixed Solvents. IV
Authors: Kondo Yasuhiko , Honjo Yoshitoshi , Tokura Niichiro
Published: July 2006

Three cases of combinations of the solvation free-energy differences in two solvents, with respect to a reactant and an activated complex, have been proposed. The theoretical expressions for the rate constant and for the activation energy in binary mixed solvents have been derived for each model. From the theoretical calculations based on these models, it has been demonstrated that the behavior of a system in which the reaction rates are mainly dependent on the difference in the solvation energies of an activated complex can be distinguished from behavior of a system where the reaction rates are controlled by the difference in the solvation energies of a reactant. The reaction rates of the Menschutkin reaction in binary mixed solvents containing liquid sulfur dioxide as one component of the mixed solvent have been analyzed on the basis of these models.
The Extraction of Uranium(VI) from Sulphuric Acid Solutions by Di-n-octylamine
Authors: Sato Taichi
Published: July 2006

The partition of uranium(VI) between sulphuric acid solutions and solutions of di-n-octyl-amine (DOA) in benzene has been investigated at different concentrations of sulphuric acid, solvent and aqueous uranium, and at different temperatures. The acidity and the water content of the organic phase, and the effect of the organic solvent on the extraction have also been examined. An infrared spectral study has been made of the organic solutions. The mechanism of the extraction of uranium from sulphuric acid solutions by DOA is discussed on the basis of the results obtained, and a composition is proposed for the complex formed in this extraction system.
Polarographic Behavior of Tris(2,2′-bipyridine)chromium(III) and Tris(ethylenediamine)chromium(III) in Acetonitrile Solutions
Authors: Sato Yuichi , Tanaka Nobuyuki
Published: July 2006

Polarographic behavior of tris(2,2′-bipyridine)chromium(III) perchlorate and tris(ethylenediamine)chromium(III) perchlorate in acetonitrile solutions has been investigated by the measurement of d.c., a.c. and Kalousek polarograms. The bipyridine complex gives a six-step reduction wave when tetraethylammonium perchlorate is used as supporting electrolyte. The limiting currents of the first four steps are all diffusion-controlled, and each of them is of a one-electron reduction process. It has been proposed that at the fourth step univalent tris(2,2′-bipyridine)-chromate anions, [Cr(bipy)3]−, are formed at the electrode surface in acetonitrile. The limiting current of the one-electron reduction wave of tris(ethylenediamine)chromium(III) is increased upon the addition of 2,2′-bipyridine. It was explained as a reduction of an electroactive species, Cr(II)-bipyridine complex, which was formed by the reaction between Cr(II) produced by the reduction of tris(ethylenediamine)chromium(III) complex and 2,2′-bipyridine at the electrode surface.
Catalysis in Peptide Synthesis with Active Esters. I. Bifunctional Catalysis in the Aminolysis of Benzyloxycarbonyl-l-phenylalanine p-Nitrophenyl Ester in Dioxane
Authors: Nakamizo Nobuhiro
Published: July 2006

The aminolysis reaction of benzyloxycarbonyl-l-phenylalanine p-nitrophenyl ester (I) with glycine t-butyl ester (II) was kinetically investigated in anhydrous dioxane. The spontaneous reaction was confirmed to follow the equation:

d[p-nitrophenol]⁄dt=kobs[I]=(k0+kamine[II])[I][II]

The catalytic actions of various additives were studied at a 2×10−3m concentration of I and II, where the amine-catalyzed term could be neglected. Of the many additives, only carboxylic acids and α-pyridone were effective as catalysts. The catalytic effect apparently decreased in the sequence: trimethylacetic acid>acetic acid>α-pyridone>monochloroacetic acid. For these catalyses, a bifunctional, concerted mechanism was proposed which involves an 8-membered transition state.
The Surface Structure of Silica Gel Studied by Dielectric Dispersion
Authors: Kondo Seiichi , Muroya Masa-aki
Published: July 2006

The effect of water adsorption and heat treatment at various temperatures between 200 and 1100°C on the dielectric dispersions of silica gel was measured in the frequency range from 50 to 3×106 Hz and 9.81 GHz and in the temperature range from −196°C to 180°C. Two anomalous dispersions (Dispersion I and II) and one anomaly (Anomaly III) were found. The mechanisms of those anomalies were discussed in relation to some physical properties and silica crystal structures. Dispersion I, having activation energy ΔE equal to 11 to 14 kcal/mol, can be ascribed to the monomolecular layer of adsorbed water. Dispersion II, with activation energy of about 5 to 7 kcal/mol, can be attributed to proton diffusion through hydrogen-bond chain of surface silanol groups. Anomaly III, having activation energy of about 3 kcal/mol, may be assigned to dipolar rotation of free silanol.
The Micellar Properties of Disodium Monoalkyl Phosphates in Aqueous Solutions
Authors: Tahara Takashi , Satake Iwao , Matuura Ryohei
Published: July 2006

The disodium monoalkyl phosphate with n-dodecyl, n-tetradecyl and n-hexadecyl radical was synthesized, and pNa and light scattering studies were performed on the micellar properties of these surfactants in aqueous solutions. The critical micelle concentrations (CMC) of these salt solutions were confirmed to be considerably higher than those of ordinary 1–1 type ionic surfactants with the same alkyl chain length. The degree of dissociation of the micelle was, however, found to be not so different from that of corresponding sodium alkyl sulfate. The fact that these salts have comparatively large aggregation number reflects one of the characteristic features of alkyl phosphate anion which has two dissociable groups.
Coulometric Titration of a Microamount of Water after Conversion to Ammonia
Authors: Yoshimori Takayoshi , Ishiwari Syuiti
Published: July 2006

Sodium amide was used to convert a microamount of water into ammonia in a carrier gas. The ammonia was then titrated with coulometrically generated hypobromite ions. The reaction between water and sodium amide was completed stoichiometrically, and the reaction rate was considerably promoted by heating sodium amide at 80°C. The sample hydrogen was oxidized with copper(II) oxide at 800°C, and the water thus produced was determined by this method. 0.096–0.665 ml (8.6–59.8 μg) of hydrogen and 0.055–0.465 mg of water in barium chloride crystals were determined within errors of 3.6% and 3.0% respectively. The water adsorbed on the surfaces of the weights was also determined by this method at various humidities.
The Separation of Hexacyanoferrate(II) and Hexacyanoferrate(III) Ions by Reversed-phase Partition Chromatography
Authors: Akaza Ikuko , Kiba Toshiyasu , Taba Minoru
Published: July 2006

The separation of hexacyanoferrate(II) and (III) ions with a TBP-HCl extraction system has been carried out by reversed-phase partition column chromatography. TBP adsorbed on Kel-F powder was used as the stationary phase in the column. Elution was performed with hydrochloric acid of various concentrations and with water, both having been saturated with TBP. The actual separation of hexacyanoferrate(II) and (III) ions from each other was successfully achieved, even in a large volume of a sample solution, by carrying out the elution with 3n HCl. The dependencies of the distribution ratio on the acidity of the solution and on the concentration of TBP in the stationary phase were examined on the basis of the elution curves under various conditions. The liquid-liquid batch extraction was also carried out under the same conditions; it was found an identical relation of distribution between the two phases held in both column and batch extractions. The principal extracted species might be assumed to be a large ion-pair hydrated and solvated.
Graft Copolymerization onto Cellulose in Dimethyl Sulfoxide by Means of a Ceric Salt Containing Lauryl Sulfuric Ions
Authors: Kaeriyama Kyoji
Published: July 2006

Styrene was polymerized in dimethyl sulfoxide by alcohol-ceric salt containing lauryl sulfuric ions. The rate of polymerization increased with the amount of ethyl alcohol added. A deuterium isotope effect was observed when tetradeuteromethyl alcohol was used as an initiator. Accordingly, the generation of radicals by the elimination of the hydrogen atom from the alcohol molecule was concluded. When styrene was polymerized in the presence of cellulose, graft copolymer was obtained. The grafting efficiency amounted to about 70%.
Synthesis and Physical Properties of Long Chain Compounds. X. Studies on the X-Ray Diffraction Patterns of Normal Higher Primary Amines
Authors: Watanabe Akira , Ishizawa Akio , Kosaka Masao , Got\={o} Ry\={o}z\={o}
Published: July 2006

For the members of n-higher primary amines from C12 to C20 the crystal structure was studied by X-ray powder method. From the values of long spacings and the splitting of (110) reflections it was concluded that the structure is probably similar to that of fatty acids and that the hydrocarbon chains are tilted with respect to the plane formed by end groups. This structure seems to be stable over the temperature range between room temperature and melting points. The dependence of melting points on chain length was discussed.
Reaction of Acyl Oxime with Mercaptan
Authors: Sudo Rokuro , Kaneda Akira , Furuoya Nobuo
Published: July 2006

The acyl derivative of oxime, derived from a strong acid, is generally unstable. However, acyl oximes of the ethyl α-oximinoacetate derivative were prepared and were found to be more stable than ordinary acyl oxime. Acetyl, carbethoxy, benzoyl, and even tosyl ester were prepared, and their reactions with the mercaptide anion were investigated.
Reaction of Vetivazulene with Sulfur. 3,5,9-Trimethylazuleno-[1,2-b]thiophene
Authors: Hayashi Shûichi , Kurokawa Shinji , Matsuura Tamon
Published: July 2006

Vetivazulene was heated with sulfur to give a new sulfur-containing azulene, 3,5,9-trimethylazuleno[1,2-b]thiophene. On Vilsmeier formylation, the compound normally resulted in the formation of 4-formyl derivative, while the acetylation according to the Vilsmeier procedure proceeded abnormally to produce 4-dimethylamino-3,5,9-trimethylazuleno[1,2-b]thiophene.
Syntheses of Pterocarpans. II. The Synthesis of (±)-Pterocarpin
Authors: Fukui Kenji , Nakayama Mitsuru
Published: July 2006

The reduction of medicagol methyl ether with lithium aluminum hydride in tetrahydrofuran yielded a diol. The dehydration of the diol in boiling diethylene glycol gave an ether (anhydropisatin, O-methyl anhydrosophorol). Then, the above ether was hydrogenated with 10% Pd-C to (±)-pterocarpin.
A Cationic Polymerization of Formaldehyde in Liquid Carbon Dioxide. V. Reaction Mechanism
Authors: Yokota Hisao , Kondo Masatsune , Kagiya Tsutomu , Fukui Kenichi
Published: July 2006

The present work was carried out in order to elucidate the reaction mechanism in the polymerization of formaldehyde in liquid carbon dioxide. Methylene glycol methylether acetate with a structure similar to that of methylene glycol monocarboxylate, which was assumed to be an initiator, exhibited a catalytic activity. On the other hand, methyl acetate terminated the polymerization. Moreover, the resulting polymer, which was terminated by the addition of methyl-2H3-acetate, contained deuterium originating from the terminator used. On the basis of these experimental results, a reaction mechanism of the elementary processes is discussed.
Photoemission from Polycyclic Aromatic Crystals in the Vacuum Ultraviolet Region. III. Aromatic Crystals and Charge-transfer Complexes
Authors: Hirooka Tomohiko , Kochi Masakatsu , Aihara Jun-ichi , Inokuchi Hiroo , Harada Yoshiya
Published: July 2006

The photoemission from various types of charge-transfer complexes, quinolinium-tetra-cyanoquinodimethane Q(TCNQ2 (I), dibenzophenothiazine (DBP)-dicyanodichloro-p-benzoquinone (DDQ)[(DBP)(DDQ)(II) and (DBP)2(DDQ)(III)], trinitrobenzene (TNB)-coronene (IV), and TNB-perylene (V),and also large polycyclic aromatic hydrocarbons, violanthrene A (VI), violanthrene B (VII), coronene (VIII), pyranthrene (IX), and pyranthrone (X), was observed in the vacuum ultraviolet region. The experimental equation Y ∝(E–E*)3, where Y is the quantum yield of photoemission; E, the incident photon energy, and E*, the threshold energy, was used to determine the ionization potential. The E*-values, as estimated from the experimental equation, were I=4.85 eV, II 4.99, III 4.75, IV 5.62, V 5.52, VI 5.06, VII 5.13, VIII 5.58, IX 5.04, and X=5.71 eV. A band structure scheme for these organic semiconductors was introduced to analyse the emission mechanism.
Infrared Spectra of Biuret-hydrate and Its Deuterated Compound
Authors: Uno Toyozo , Machida Katsunosuke , Saito Yutaka
Published: July 2006

The infrared spectra between 4000 and 33 cm−1 of biuret-hydrate and between 4000 and 250 cm−1 of its deuterated compound have been recorded. The vibrational assignments have been made by referring to the infrared spectra of the related compounds and the isotopic frequency shift. Normal coordinate analysis of the in-plane vibrations of biuret and biuret-d5 as twelve-body problem has been carried out by using the molecular model of the planar trans-cis conformation. A simple Urey-Bradley force field has been employed and the force constants have been refined by the least squares method. The calculation of potential energy distributions has shown that the NH in-plane deformation and the CN stretching vibrations couple appreciably with each other and give the imide II and III bands at 1515 and 1365 cm−1, respectively, just as in the case of diacetamide.
Scandium Content of Igneous Rocks and Some Oceanic Sediments
Authors: Shimizu Tsuneo
Published: July 2006

Based on the analyses of 105 individual samples and 5 composites, totaling 158 rock samples, the following averages of scandium for various types of Japanese igneous rocks have been obtained (in ppm): granites 5.6, granodiorites 7.4, liparites 6.1, quartz diorites and diorites 11.4, dacites 14.1, andesites 21.8, gabbros 26.9, basalts 27.2 and ultramafic rocks 9.5. Scandium is determined by a combined ion-exchange-spectrophotometric method. Using Poldervaart’s suggested ratio of rock types, an abundance figure of 17 ppm Sc for the crust is suggested. The results on the abundance values for scandium in various types of igneous rocks confirm generally the figures given by Norman and Haskin in 1968. Analyses are also performed on Pacific oceanic sediments, giving as averages 18.7 ppm Sc for 4 red clays, 12.1 ppm Sc for 2 volcanic muds and 13.1 ppm Sc for 2 globigerina oozes. Brief discussion on the geochemistry of scandium is given.
The Alkaline Ethanolyses of Chlorophenyldiphenylsulfonium Halides, Chlorophenyl Phenyl Sulfones and Chloronitrobenzene in Aqueous Ethanol
Authors: Oae Shigeru , Khim Yong He
Published: July 2006

o-, m-, and p-Chlorophenyldiphenylsulfonium halides were prepared and subjected to the alkaline ethanolysis in order to compare the activating effects of o-, m-, and p-diphenylsulfonio groups with those of o-, m-, and p-phenylsulfonyl and nitro-groups. The diarylsulfonio group at either ortho or para position was found to facilitate the nucleophilic substitution of aryl chloride powerfully. While the effect of diarylsulfonio group was not only substantially larger than that of phenylsulfonyl group, but also exceeding even that of nitro group. Meanwhile, with ethoxide ion in ethanol the alkaline decomposition reaction, presumed to be initiated by the attack of ethoxide on the sulfur atom of chlorophenyldiphenylsulfonium halide, occurred competitively along with the SN reaction, but the rate of the SN reaction of p-chlorophenyldiphenylsulfonium perchlorate was found to be about 9 times larger than that of the decomposition reaction. Substitution of a methyl group at ortho to diphenylsulfonio, phenylsulfonyl and -sulfinyl groups did change very little the rates of the ethanolyses of the corresponding p-substituted chlorobenzenes, suggesting that essentially there is no or little steric inhibition for the 3d-orbital resonance with either sulfonio, sulfinyl, or sulfonyl group in the SN reaction of these compounds.
Studies on Stable Free Radicals. II. Reactivity of Stable Nitroxide Radicals and NMR Spectra of Reaction Products
Authors: Murayama Keisuke , Morimura Syoji , Yoshioka Takao
Published: July 2006

We have isolated coupled products of such stable free radicals as 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (II), cyclohexane-1-spiro-2′-(4′-oxoimidazolidine-l′-oxyl)-5′-spiro-l″-cyclohexane (IV) and 2,2,6,6-tetramethyl-4-oxopiperidine-1-thiyl derived from bis-[2,2,6,6-tetramethyl-4-oxopiperidyl-(1)]disulfide (VII) with a C-radical derived from α,α′-azo-bis(isobutyronitrile). The reactive site in these stable free radicals was studied from the structure of the coupled products. The homolysis of the disulfide (VII) appeared to be accelerated by an attack of the C-radical, 1-methyl-1-cyanoethyl. The NMR spectra of the products suggested a slow inversion of the nitrogen atom in piperidine derivatives.
Thermal Decomposition of 1,1-Disubstituted-3-aryl-3-(aryloxythiocarbonyl)-2-thioureas
Authors: Miyazaki Koshin
Published: July 2006

1,1-Disubstituted-3-(4-chlorophenyl)-3-(phenoxythiocarbonyl)-2-thioureas of the formula R,R′N–C1(=S)–N(p-Cl–C6H4–)–C′(=S)–OC6H5 (II), when kept at an elevated temperature without any solvent, decomposed into the corresponding thionocarbamates of the formula R,R′N–C(=S)–OC6H5 (III), while p-chlorophenyl isothiocyanate was eliminated. A carbon-14-labeling experiment showed that the decomposition proceeded only through the following path:

II→R,R′N–C2(=S)–OC6H5+p-Cl–C6H4–N=C1=S

Kinetic studies of the various II showed that the decompositions were strictly first order. The rate constant at 175°C increased in the order: R,R′=(CH3)2>(C2H5)2>CH3,4-methylbenzyl\gtrsim (n-C3H7)2>CH3, benzyl>CH3, 4-chlorobenzyl. Neither the products nor the rate of the decomposition reaction was influenced by the presence of a radical scavenger. Furthermore, a crossover decomposition reaction did not give any crossover products. On the basis of these results, a possible intramolecular mechanism of the decomposition involving a four-membered cyclic intermediate structure was proposed.
The Solvent Effects in the Acylation of Alcohol. The Effects of Liquid Sulfur Dioxide on the Dissociation of Hydrogen-bonded Alcohol
Authors: Nagai Toshikazu , Abe Hironobu , Tokura Niichiro
Published: July 2006

The reason for the rate-enhancing effect of liquid sulfur dioxide on the rate of the benzoylation of methanol has been studied. The observation of the NMR spectra revealed that the amount of the hydrogen-bonded methanol is decreased (but not completely eliminated) by sulfur dioxide in the liquid SO2-CCl4 system. The existence of a correlation between the rates of esterification and the dissociation of the associated alcohol accounts for the role of the sulfur dioxide as the agent for the dissociation of the methanol-hydrogen bonding during the esterification.
A Kinetic Study on the Homogeneous Liquid-phase Oxidation of Cumene in the Presence of Triphenylsulfonium Chloride
Authors: Ohkubo Katsutoshi , Yamabe Tokio , Fukui Kenichi
Published: July 2006

A kinetic study of the homogeneous liquid-phase oxidation of cumene was carried out in order to clarify the characteristic behavior of triphenylsulfonium chloride as an autoxidation catalyst. The reaction proceeded with no incubation period. The experimental dependence of the rate upon catalyst and hydrocarbon concentrations and also upon the oxygen pressure was reproduced with a good analytic fit by the following equation:

r=k′(RH)1.27(O2)0.68(Cat.)0 (e−at−e−bt) (a, b, and k′ are constants).

A reaction mechanism was proposed to derive the rate equation. It seems likely from this scheme that sulfonium chloride activates molecular oxygen by means of a reversible molecular association with it.
Studies of Acenaphthene Derivatives. XVI. The Wittig Reaction with Acenaphthenequinone
Authors: Tsuge Otohiko , Tashiro Masashi , Shinkai Ichiro
Published: July 2006

The reactions of acenaphthenequinone (III) with several Wittig reagents have been studied. When III was reacted with equimolar amounts of benzylidenetriphenylphosphoranes (IV) at room temperature, the corresponding benzylideneacenaphthenones (V) were obtained in fairly good yields, but the reactions of benzil and phenanthrenequinone with IV did not take place under similar conditions. The reaction of III with two equivalents of IV under severe conditions afforded only V, and no dibenzylidene compounds were obtained. The reaction of III with resonance-stabilized phosphoranes, such as acetonylidene-, phenacylidene- and p-chlorophenacylidenephosphoranes, afforded the expected α,β-unsaturated ketones. In the reaction with ethoxycarbonylmethylenephosphorane, two stereo-isomeric ethoxycarbonylmethyleneacenaphthenones, which were also obtained from the reaction with diethyl ethoxycarbonylmethylphos-phonate, were formed. The structures of the isomers were confirmed on the basis of NMR, UV, and mass spectral studies. Methylenephosphorane reacted with III to give methyleneacena-phthenone in a poor yield. On the contrary, the reaction with ethylidenephosphorane gave bis-2,2′-methyleneacenaphthenone, which was also formed by the reaction of acenaphthenone with glyoxal, in a good yield.
Studies of Acenaphthene Derivatives. XVII. The Reaction of Benzylideneacenaphthenone with Hydrazines
Authors: Tsuge Otohiko , Shinkai Ichiro , Tashiro Masashi
Published: July 2006

The reactions of benzylideneacenaphthenones with hydrazines are reported. The reaction of benzylideneacenaphthenone with hydrazine hydrate in methanol at 40°C gave 1-hydroxy-2-hydrazinobenzylacenaphthylene, which was then cyclized to the 1-acetylpyrazoline by treating it with acetic anhydride. The hydrazino compound reacted with phenyl isocyanate to give the 1:2-adduct, which, when then treated with hydrochloric acid, suffered ring closure to the pyrazoline compound. Under severe conditions with hydrazine hydrate, however, the reductive cleavage reaction took place, giving the hydrazones of both acenaphthenone and benzaldehyde. Similar phenomena were also observed in the reaction with p-substituted benzylideneacenaphthenones. On the other hand, the reaction with phenylhydrazines in ethanol containing sulfuric acid afforded directly the expected pyrazolines, from which pyrazoles were then prepared by treating them with lead tetraacetate. Furthermore, the corresponding pyridazine was formed in the reaction of phenacylideneacenaphthenone with hydrazine hydrate, while the reaction with 2,4-dinitrophenyl-hydrazine gave the pyrazoline compound.
Electronic Absorption Spectra of Unstable Species Formed by the Ultraviolet Irradiation of N,N-Dimethylaniline at 77°K
Authors: Arimitsu Satoshi , Kimura Katsumi , Tsubomura Hiroshi
Published: July 2006

Electronic absorption spectra of unstable species formed by the ultraviolet irradiation of N,N-dimethylaniline (DMA) were studied in various rigid matrices at 77°K. It was concluded that there are two unstable species which exhibit similar absorption spectra in the visible and the near ultraviolet regions. These species were identified with the cation radical ([(Remark: Graphics omitted.)])+ and the neutral radical ((Remark: Graphics omitted.)), based on various experimental results concerning solvent effect, electron attachment, stimulated emission by the infrared light, etc. The molar extinction coefficient of the cation at 470 mμ was found to be about 1200 (l/cm·mol).
Raman Effect in Ferroelectric Sodium Nitrite Crystal. II. Dependence of B2 Type Phonon Spectrum on Propagation Direction
Authors: Tsuboi Masamichi , Terada Minoru , Kajiura Teruo
Published: July 2006

The Raman spectra corresponding to the (bc) component (B2 type vibrations) of the polarizability tensor in the ferroelectric sodium nitrite crystal (C2v20) have been observed with various directions of the phonon propagation. It has been found that one of the B2 Raman lines at 160 cm−1 splits into two components when the phonon propagates in a direction 45° from the c axis in the ac plane. This splitting has been ascribed to an interaction of a B2 and B1 type lattice-vibrations whose frequencies are accidentally equal to each other in the phonon propagation direction now in question.
New Methods of Preparing the Mixed Cyano Cobalt (III) Complexes
Authors: Maki Nobufumi , Sakuraba Shukichi
Published: July 2006

The following new cyano cobalt(III) complexes have been prepared by treating the corresponding chloro complexes with silver cyanide: cis-[Co(CN)2dip2]NO3·7H2O, cis-[Co(CN)2dip2]2-SO4·12H2O, cis-[Co(CN)2en(NH3)2]NO3, [Co(CN)3en(NH3)]·H2O, and trans-[Co(CN)dg2(NH3)]·1/2H2O. This method has also been used in the preparation of the following compounds: cis-[Co(CN)(NO2)en2]NO3·H2O, cis-[Co(CN)(SO3)en2], trans-[Co(CN)(SO3)en2], cis-[Co(CN)-(OH2)en2]SO4·2H2O, cis-[Co(CN)2en2]NO3, cis-[Co(CN)2pn2]NO3, cis-[Co(CN)2phen2]NO3· 6H2O, and cis-[Co(CN)2phen2]Cl·4H2O. Another new method has been attempted in dimethyl sulfoxide or an acetonitrile-water solution by the step-by-step substitution of a chloro ligand with a CN− ion via the monocyanomonochloro complex of the [Co(CN)Cl N4]-type; we thus succeeded in obtaining these dicyano-ammine complexes, trans-[Co(CN)2(NH3)4]NO3·H2O, trans-[Co(CN)2-en(NH3)2]Cl·H2O, and cis-[Co(CN)2(NH3)4]NO3·H2O. The methods of preparing the following new complexes are also described: trans-Na[Co(CN)2dg2]·2H2O, trans-K[Co(CN)2dg2]·3/2H2O, trans-(NH4)2[Co(CN)dg2(SO3)]·4H2O, and trans-H[Co(CN)dg2Cl]·4H2O. The absorption spectra in the visible, ultraviolet, and infrared regions have been measured.
The Chemistry of Protactinium. VII. The Stability of Protactinium (V) in Perchloric Acid and TTA-Benzene Solutions
Authors: Suzuki Shin , Inoue Yasushi
Published: July 2006

With a view to understand the reasons for the confusion in published works as to the chemical behavior of protactinium (V) in a perchloric acid solution, the effect of the contact time and the stability of the perchloric acid solution of the pentavalent protactinium in the TTA-benzene extraction have been investigated in relation to the methods of preparing the solution. Four sample solutions, prepared by various methods, were used, and definite differences among them were observed. Two of them have been confirmed to be very stable and not to suffer a change in their distribution ratios with the time of standing, while the others are unstable-that is, their distribution ratios decrease with standing, thereby reaching a constant value which agrees with that of the former two. However, the value consistent with that obtained from backward extraction is not this constant value but the value obtained from fresh solutions of the latter type. Protactinium species in the TTA-benzene solution are also not stable, and their distribution ratios increase with standing. This increase in the distribution ratio is mainly due to the formation of unstrippable species. The mechanism of this irreversible change is assumed, from the indirect evidence of extraction experiments and absorption spectroscopy, to be the irreversible dehydration of Pa(OH)2T3·HT to form PaOT3·HT in the organic phase. These unfavorable features of the extraction equilibrium should be taken into account in interpreting the results obtained by TTA extraction experiments.
Proton NMR Studies of Substituent Effects. The Hammett-type Relationship in meta- and para-Substituted Formanilides
Authors: Niwa Jun
Published: July 2006

The spectral analyses of 23 meta- and para-substituted formanilides in dimethyl sulfoxide have proved that they exist in an equilibrium of cis- and trans-forms of restricted rotational isomers in the solvent. The chemical shifts of the protons on the formanilides are strongly dependent on the polar nature of the substituent. In the cis-form, the chemical shifts of both the imino and the formyl protons correlate with the Hammett σ0. In the tarns-form, a plot of the chemical shifts of the formyl protons against the σ0-constants reveals a good correlation in the case of meta-derivatives, but serious deivations for the para-substituents, both for the electron-releasing conjugative substituents and for the electron-withdrawing conjugative substituents. The deviations for both types of substituents are in the direction to be anticipated for any important extra conjugative interaction between the para-substituent and the side-chain. The Yukawa-Tsuno equation is precisely applicable to these shifts when we assume that this system has the same γ-value for both types of substituents; the relation is expressed as:

Δδ=−12.0(σ0+1.12Δ\barσR)+0.5.

where Δ\barσR=σ+−σ0 for the electron-releasing conjugative substituents and where Δ\barσR=σ+−σ0 for the electron-withdrawing conjugative substituents (r=0.993, s=0.8). From the solvent effect on the substituents, such as NH2, OH, and COOH, their σ0-values in dimethyl sulfoxide are proposed. It is also deduced that this solvent effect affects principally the part of the inductive contribution in the overall substituent effect.