bluuebunny/crossref_metadata_2025 huggingface dataset:
Melting and Solid–Solid Transition Temperatures at High Pressures for NH4SCN, RbSCN, T1SCN, and CsSCN
Authors: Klement William
Published: July 2006

Differential thermal analyses at high pressures have yielded the following trajectories for melting and solid–solid transitions in the several thiocyanates: (substance, transition, 1-bar transition temperature in °C, initial slope (dT/dp) in deg kbar−1, initial curvature (–d2T/dp2) in deg kbar−2, approximate maximum pressure in kbar) NH4SCN, melting, ≈146, ∼20 (tentative), –, ∼3.5; NH4SCN, (upper) solid–solid, 120±4, 12.6±1.5, –, 7.5; RbSCN, melting, 184±2, 15.7±0.3, 0.32±0.05, 36; RbSCN, solid–solid, 166±3, 13.5±1.0, 0.3±0.1, 30; TlSCN, melting, ≥234, ≥10 (tentative) >0, 34; TlSCN, solid-solid, 99±2, 9.6±1.0, ≈0.17, 34; CsSCN, melting, ≥206, ≈14±1.5, ∼0.2–0.4, 33; CsSCN, solid-solid, ≥197, ≈11.8±1.0, ∼0.2, 33. The solid–solid transitions investigated here for NH4SCN, RbSCN and T1SCN appear to be closely-related, structurally, to the well-investigated transition in KSCN. The thermodynamics of the KSCN transition at 1-bar is discussed anew so as to be consistent with high pressure data. The transitions in these other thiocyanates are probably thermodynamically similar to the KSCN transition but the necessary data to establish the similarities are lacking. Lattice parameters for NH4SCN and RbSCN show rapid variations with temperature below the solid–solid transition, as for KSCN. DSC and DTA results are presented for the 1-bar transition temperatures and entropy changes for NH4SCN, RbSCN, TlSCN, CsSCN and also AgSCN. The entropy changes apparently associated with the structurally similar solid–solid transitions decrease with increasing cation polarizability.
The Electronic Spectra of Some Phenylthiophenes. A Molecular Orbital Treatment
Authors: Abu-Eittah R , Hilal R
Published: July 2006

The electronic absorption spectra of the thiophene derivatives: mono, di-, and poly-phenylthiophenes are studied in both polar and non-polar solvents. The interaction between thienyl and phenyl chromophores is investigated both experimentally and theoretically. Assuming planar and perpendicular conformers, molecular orbital calculations are carried out on 2-phenylthiophene and on 3-phenylthiophene using the Localized-Orbital Model. The results show: (i) the planar conformer is more adquate than the perpendicular one, (ii) the near UV spectra of the two isomers are similar though their degree of conjugation is different, and (iii) excited states arise from substantial configuration interaction. There is a good agreement between the observed and calculated spectra of the two isomers.
Proton Magnetic Resonance Study of Poly(p-chlorostyrene) of Low Molecular Weight
Authors: Hirai Yoshiyuki , Nunomura Yoshio , Imamura Yoshio
Published: July 2006

Poly(p-chlorostyrne) samples of relatively low molecular weight (average degrees of polymerization (‾DP): 15, 24, and 46) were prepared by radical polymerization and their PMR spectra were observed in the temperature range 5–88 °C. When the temperature was elevated, the absorption of the methyne proton moved to lower field and the half height width for the absorption of the ortho proton decreased more remarkably than that of the meta proton. The absorption of the ortho proton of one polymer sample (‾DP: 15) showed an anomalous broadening. These features of the observed spectra were interpreted in terms of ring current shielding by aromatic side groups, and the conformations of the polymer are discussed.
Studies on 1,2,4-Thiadiazolidine Derivatives. I. The Synthesis and Structural Determination of 2,4-Disubstituted 3,5-Disubstituted Imino-1,2,4-thiadiazolidines
Authors: Kinoshita Takeshi , Sato Sadao , Tamura Chihiro
Published: July 2006

The reaction of symmetrical thiourea derivatives, RNHCSNHR, with benzoyl peroxide (BPO) gave only one isomer of 2,4-disubstituted 3,5-disubstituted imino-1,2,4-thiadiazolidines, and that of nonsymmetrical thiourea derivatives, RNHCSNHR′, with BPO yielded a mixture of some of the possible isomeric derivatives. The structures of these compounds were determined by means of NMR, mass spectra, and X-ray analyses. The steric effects of peripheral groups around the thiadiazolidine ring and some reaction mechanism are discussed.
Studies of Sulfonyl Radicals. III. Solvent Effects on the Thermal Decomposition of Benzyl Phenylazo Sulfone
Authors: Iino Masashi , Yanagisawa Tateo , Takahashi Yozo , Matsuda Minoru
Published: July 2006

The first-order rate constants for thermal decomposition of benzyl phenylazo sulfone (BPA, 1) have been determined spectrophotometrically in six solvents using the free radical scavenging technique with a stable Koelsch free radical. Activation parameters in the non-polar solvents such as benzene, toluene, anisole and chlorobenzene were almost the same, but in the two polar solvents, pyridine and nitrobenzene, activation entropies decreased significantly as compared with those in the non-polar solvents. This can be explained by the solvation of the polar solvent in the transition state leading to a phenyldiazenyl and α-toluenesulfonyl radical pair.
The Reaction of Organoboranes with d-Carvone and l-Perillaldehyde in the Presence of Oxygen. Evidence for a Coordination between Organoboranes and α, β-Unsaturated Carbonyl Oxygens in Their Oxygen-Induced Free Radical Reaction Process
Authors: Arase Akira , Masuda Yuzuru , Suzuki Akira
Published: July 2006

Oxygen-induced 1,4-addition reactions of trialkylboranes with cyclic α, β-unsaturated carbonyl compounds were studied. Stereoselective 1,4-additions of the alkyl groups of trialkylboranes were observed in the reactions of d-carvone and l-perillaldehyde. Namely, it was shown that the alkyl group adds to d-carvone from the trans side with respect to isopropenyl group to give the corresponding saturated ketones. The same type of one side attack of the alkyl group to l-perillaldehyde was also observed. The evidence seems to strongly support the hypothesis that coordination of boron atoms of trialkylboranes to carbonyl oxygens plays an important role, even in the oxygen-induced free radical chain reaction of organoboranes with α, β-unsaturated carbonyl compounds.
A Synthesis of Diosphenols
Authors: Ohashi Masao , Inoue Seiichi , Sato Kikumasa
Published: July 2006

A new synthesis of diosphenols (1 and 2) is described. The oxidation of 2-isopropylcyclohexanone with copper(II) chloride gave the corresponding α-diketone (8), which was then methylated to afford diosphenol (1) together with a considerable amount of isodiosphenol (2). In particular, pure 2 has been isolated and the characteristics of 2 are also presented.
The Abnormal Wallach Rearrangements of 4,4′-Dialkylazoxybenzenes
Authors: Shimao Ichiro , Matsumura Shigenori
Published: July 2006

The reactions of 4,4′-dialkylazoxybenzenes (1) with sulfuric acid afforded 2-alkyl-5-(p-alkylphenylazo)phenols (2) and 2-alkyl-4-(p-alkylphenylazo)phenols (3) as novel rearrangement products; in certain cases 4-(p-alkylphenylazo)phenols (4) were also obtained. The ratios of these azophenols were greatly affected by the alkyl group type. In addition, the reactions gave a very small amount of 5-alkyl-2-(p-alkylphenylazo)phenols (5), which were considered as normal Wallach rearrangement products.
The Facile Synthesis of N-Substituted Piperidines from Glutaraldehyde and Primary Amines with Tetracarbonylhydridoferrate
Authors: Watanabe Yoshihisa , Shim Sang Chul , Mitsudo Take-aki , Yamashita Masakazu , Takegami Yoshinobu
Published: July 2006

Ethanolic tetracarbonylhydridoferrate solution combined with glutaraldehyde is very efficient for the selective transformation of an amino group into a piperidine ring. A large variety of both aliphatic and aromatic amines react with the ferrate-glutaraldehyde at room temperature under carbon monoxide to give the corresponding N-alkyl- and N-arylpiperidines in good to excellent yields.
Dehydroannulenes. V. Synthesis and Properties of 1,6,12,17-Tetra-t-butyl-2,4,13,15-tetrakisdehydro[22]annulene
Authors: Iyoda Masahiko , Miyazaki Hideaki , Nakagawa Masazumi
Published: July 2006

The synthesis of 1,6,12,17-tetra-t-butyl-2,4-13,15-tetrakisdehydro[22]annulene has been performed. The tetrakisdehydro[22]annulene was found to be strongly diatropic having high conformational stability.
Pseudohalogen Chemistry. III. Orientation of Heterolytic Addition of Thioeyanogen Chloride to Some Unsymmetrical Alkenes
Authors: Guy Robert G , Pearson Ian
Published: July 2006

Thiocyanogen chloride reacts with various unsymmetrical alkenes, cycloalkenes, and α-arylalkenes in the presence of a radical inhibitor in acetic acid in the dark at 25 °C to yield α-chloro-β-thiocyanates, α-acetoxy-β-thiocyanates, α-hydroxy-β-thiocyanates, vinylic thiocyanates or allylic isothiocyanates in various combinations. The additions to the α-arylalkenes are regiospecific, yielding the Markownikov-orientated products, but the regiospecificity of the additions to the aliphatic alkenes depends on the structure of the alkene. The orientation of addition is discussed in terms of open carbonium ions, e.g.  17, for the α-arylalkenes and cyano-sulfonium ions, e.g.  18, for the aliphatic alkenes.
Dielectric Transition in a Solution of Linear Poly(vinyl acetate)
Authors: Mashimo Satoru , Iwasa Yasuo , Chiba Akio , Higasi Keniti
Published: July 2006

The dielectric constants and losses of linear poly(vinyl acetate) (PVAc) in carbon tetrachloride were measured at various temperatures and frequencies. The results provide proof that dielectric transition in solution occurs for PVAc, irrespective of its sources.
Benzene Induced Shift for Some Organometallic 8-Quinolinolato Complexes: A New Criterion for the Interaction of Nitrogen with Metal
Authors: Kawasaki Yoshikane
Published: July 2006

The benzene induced shift was measured for some organometallic 8-quinolinolato complexes. A large upfield shift (0.5–0.7 ppm) of the 2-proton of the 8-quinolinolato ligand was found in benzene when the nitrogen in the 8-quinolinolato ligand coordinated to the metal. But the shift was small (0–0.3 ppm) in the absence of nitrogen coordination.
Stability Constants of the Rare Earth Complexes with 2-Ethyl-2-hydroxy-3-methylbutyric Acid
Authors: Suzuki Yasuo , Powell Jack E
Published: July 2006

The stability constants of the rare-earth complexes with 2-ethyl-2-hydroxy-3-methylbutyric acid have been determined potentiometrically at 25.0 °C and at an ionic strength of 0.10, with sodium perchlorate as the supporting electrolyte.
The Reduction of Divalent Copper and Tetravalent Tellurium by Ascorbic Acid–Application to Copper Telluride Analysis
Authors: Joshi M K , Raoot Sarala
Published: July 2006

Quantitative reduction of Cu2+ to metal copper and Te4+ to metal tellurium by ascorbic acid in alkaline and acid medium respectively has been studied. Based on this a new method for easy and simultaneous determination of copper and tellurium as in copper-telluride has been developed with reproducible results.
Preparation of Hindered Esters from Acid Chlorides and Alcohols in the Presence of Silver Cyanide
Authors: Takimoto Seiji , Inanaga Junji , Katsuki Tsutomu , Yamaguchi Masaru
Published: July 2006

Sterically hindered esters were prepared from the corresponding acyl chlorides and alcohols in the presence of silver cyanide. The method is superior to the conventional acyl chloride–alcohol–pyridine method as regards yield and the rapidity of reaction.
The Simulation of the ESR Spectra of the Perylene Cation on Solid Surfaces
Authors: Ueda Hisashi
Published: July 2006

The simulation of the ESR spectra of the perylene cation formed on the surface of silica gel (with MoO3), silica–alumina, and γ-alumina (with MoO3) was studied. These oxides were pretreated in a vacuum of 10−5 Torr and at 300 °C, and were then brought into contact with a purified perylene solution in benzene. The main parameters which determine the shape of spectra were investigated. By comparing the experimental spectra with the simulated ones, it was concluded that unpaired electron-spin densities on the carbon atoms of the perylene cation are identical to those of the perylene cation in the H2SO4 solution. However, the number of γ-protons which have spin-nuclear interactions with the unpaired electron is three or less. It was found that a considerable part of the line-width is caused by g-unisotropies. If the perylene cation is bound more strongly on the surface, more g-unisotropy is observed and the half-width becomes wider. When the perylene cation is prepared in the air, O2 and H2O molecules coordinate to the perylene cation formed. It was found that the complex cations thus formed have different g-unisotropies and that the ESR spectrum of this cation mixture is structureless, smooth, and a continuous curve.
Heterogeneous Catalysis in Liquid-Phase Oxidation of Olefin. I. Activity of Vanadium System Catalysts for Oxidation of Cyclohexene
Authors: Takehira Katsuomi , Ishikawa Toshio
Published: July 2006

The catalytic activities of various binary oxides containing vanadium for the liquid-phase oxidation of cyclohexene have been studied, in comparison with those of one component oxides and soluble metal acetylacetonates. The reaction was carried out at 60 °C in benzene solvent. The distribution of reaction products suggests the occurrence of autoxidation and epoxidation when vanadium system catalysts are used. Among the binary catalysts, V–Cr and V–Mo systems showed relatively high specific activities, especially high activity being obtained by the former systems calcined at a low temperature. It seems that cyclohexene oxide is formed mainly by two successive catalytic processes, i.e., the formation of cyclohexenyl hydroperoxide by autoxidation and the selective oxidation of cyclohexene with the hydroperoxide. The machanism of epoxidation was confirmed by the reaction of cyclohexene with t-butyl hydroperoxide in the presence of V–Cr catalyst.
The Thermodynamics of Nonstoichiometric Pr1−yGdyO1.5+δ
Authors: Endo Kazuhiro , Yamauchi Shigeru , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

In order to contribute to the study of the thermodynamics of point defects in ionic crystals, the nonstoichiometry, δ, of Pr1−yGdyO1.5+δ (y=0, 0.1, 0.2, and 0.4) with a wide nonstoichiometric composition range was measured as a function of the oxygen partial pressure. Assuming that excess oxygen ions preferentially occupy Z-sites of the bixbyite structure and that the Pr3+ and Pr4+ ions are distributed on cationic sites at random, the equilibrium constant, K, was calculated for

2Pr^4++O_z^2-=2Pr^3++V_z+\frac12O_2

It was found that lnK changes with δ in the relation;

lnK=A+Bδ+Cδ^2

The parabolic dependence of lnK on δ is interpreted in terms of the changes in the energy of the defect formation and in the interaction energy between defects with the volume.
Thermal Decomposition of Dimethyl Ether in the Presence of Nitrogen Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo , Kubokawa Yutaka
Published: July 2006

The effect of NO addition on the thermal decomposition of CH3OCH3 has been studied at 500 °C. The rate of pyrolysis decreases markedly when the amount of NO is small, but increases linearly with increase in amount. Acceleration of pyrolysis was studied. Major reaction products are CH4, CH2O, CO, H2O, and N2, the minor ones being H2, N2O, and C2H6. The quantities of all the products were determined under different conditions except CH2O and H2O. It was found that the rate of formation is nearly of first order with respect to both NO and CH3OCH3. A reaction scheme is proposed. It is suggested that the rate of decomposition is nearly equal to that of the second order reaction NO+CH3OCH3→HNO+CH3OCH2.
Solid-state Properties of Evaporated Methyl Viologen
Authors: Murano Kentaro , Kamura Yusuke , Inokuchi Hiroo
Published: July 2006

The methyl viologen film evaporated at about 250 °C has a violet color, and its electronic absorption spectrum resembles that of the enzymatically reduced methyl viologen. The evaporated film becomes colorless upon the introduction of air. By means of the photoemission spectroscopical method, a very low ionization potential, 3.6 eV, was obtained for the evaporated methyl viologen film. The character of the evaporated methyl viologen is a free-radical one, and its specific resistivity is very low as compared with other organic radicals.
The Pressure and Temperature Dependences of the Second Virial Coefficients and the Chain Dimensions of Polydimethylsiloxane Solutions
Authors: Kubota Kenji , Kubo Kenji , Ogino Kazuyoshi
Published: July 2006

A new light-scattering optical cell was designed in order to perform light-scattering measurements at various temperatures and under pressures up to 400 kg/cm2. The second virial coefficients and the radii of gyration were determined at high polymer dilutions for polydimethylsiloxane in cyclohexyl bromide at 27.0, 36.5, 47.2, and 56.2 °C, in benzene and toluene at 27.0 °C, and in chlorobenzene at 30.0 °C. The method employed to determine the dimensions of the polymer is described. By a series of measurements of polydimethylsiloxane solutions, it is shown that the second virial coefficients, the radii of gyration, and the fundamental thermodynamic properties of the solutions depend on the pressure. The correlation between values of A2 and 〈S2〉1⁄2 shows that pressure influences these quantities through its effect on the polymer-solvent interaction parameter, χ or z. The values of the relative partial molar excess volume were calculated directly from the data. The obtained data were compared with the excluded volume theories and the corresponding state theories; the agreement was fair.
The Neutron Activation Analysis of Mercury in Soil
Authors: Nakano Souichi , Honboh Jukichi , Urabe Noriake
Published: July 2006

A radiochemical neutron activation procedure has been designed for the determination of mercury in soils. After the irradiation of 100 mg of soil it was decomposed with a hydrofluoric and perchloric acid mixture in a platinum crucible, and the mercury was separated radiochemically by solvent extraction from sulfuric acid·potassium iodide media into toluene, followed by precipitation as a sulfide. The radioactivity of 197Hg was measured by using a Ge(Li) detector. The chemical yield, as determined by atomic absorption spectrophotometry, was high enough, and the precision was satisfactory. The detection limit is estimated to be 1–2 ppb [(1–2)×10−10 g] by this method. The above procedure was applied to the determination of mercury in soils sampled in the Kumamoto and Minamata districts and in between.
The Syntheses and Properties of Bis(3-hydroxy-2-methyl-4-pyronato) Complexes of Bivalent Metal Ions
Authors: Morita Hideyoshi , Shimomura Shigeru , Kawaguchi Shinichi
Published: July 2006

Bis(3-hydroxy-2-methyl-4-pyronato) complexes of cobalt(II), nickel(II), copper(II), and zinc(II) have been prepared: CoL2(OH2)2, NiL2(OH2)2, CuL2, and [ZnL2(OH2)2]·1/2H2O. The 2,2′-bipyridine-(bpy) and 1,10-phenanthroline(phen) adducts of these complexes were also synthesized: CoL2(bpy), CoL2(phen), NiL2(bpy), ZnL2(bpy), and ZnL2(phen). Based on the magnetic, spectral, and thermogravimetric data, the structures of these complexes are proposed: all of the cobalt(II), nickel(II), and zinc(II) complexes are octahedral, and CuL2 is square planar. The NMR spectra of the zinc(II) complexes are discussed.
The Photolysis and Thermolysis of 3-(Diphenylhydroxymethyl)-4-(diphenylmethylene)-2-cyclobuten-1-one and Its 2-Bromo Derivative
Authors: Toda Fumio , Todo Eishiro
Published: July 2006

The photolysis of the title methylenecyclobutenone (1) and 2-bromomethylenecyclobutanone (9) in MeOH afforded 4,4-diphenyl-3-(2,2-diphenylvinyl)-2-buten-4-olide (5) and 3,3,5-triphenyl-1,3-dihydronaphtho[1,2-c]-furan-2-one (11) respectively. The photolysis of 1 and 9 in benzene, however, afforded 4,4-diphenyl-3-(diphenylvinylidene)-4-butanolide (2), and bromo-derivative of 5 (8) and 11 respectively. The thermolysis of 1 and 9 in o-xylene afforded 2 and 2-bromo derivative of 5(10) respectively. The mechanisms of these reactions were discussed. The solvent effect on the photolysis of 1 and 9 was also discussed.
Aminosugars. XXV. Synthesis of Benzyl 2-Acetamido-2-amino-2,3,4-trideoxy-α-d-arabino-hexopyranoside
Authors: Yoshimura Juji , Iwakawa Masaharu , Ogura Yoshio
Published: July 2006

As the attempted substitution of methyl 4-deoxy-2,3-di-O-mesyl-6-O-trityl-α-d-xylo-hexopyranoside with sodium azide gave the unsaturated compound: methyl 2,3,4-trideoxy-6-O-trityl-α-d-glycero-hex-2-enopyranoside (4), benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-d-mannopyranoside was used as the starting material, which was converted into benzyl 2-acetamido-2-deoxy-3-O-mesyl-6-O-trityl-α-d-mannopyranoside (10). For the deoxygenation of C-4 position, chlorination of 10 with sulfuryl chloride gave unexpectedly benzyl 3′-O-mesyl-6′-O-trityl-α-d-talopyranosid [2′,3′,4′; 4,5,6]-2-methyl-4,5-dihydro-6H-oxazine, due to the anchimeric effect of the C2-axial acetamido group. However, previous change of the conformation of 10 by the substitution of C3-mesyl group with azido group gave successfully the corresponding chloro derivative (13). Reduction of 13 with tributyltin hydride gave the corresponding 3,4-epimino derivative (14), due to participation of initially hydrogenated azido group, but, catalytic hydrogenation of 14 gave the title compound as the main product.
A New Type of Induced Decomposition. II. Decomposition of Phenylpropioloyl Peroxide and t-Butyl Phenyl-peroxypropiolate in Solution
Authors: Muramoto Nobuyuki , Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu
Published: July 2006

Decomposition of phenylpropioloyl peroxide and t-butyl phenylperoxypropiolate in cumene, toluene, and cyclohexane was investigated. Product analysis and kinetic study together with the findings that radicals separately generated caused the decomposition of these peroxides demonstrate of a new type of induced decomposition involving radical attack on the triple bond of these peroxides and subsequent β-scission.
A New Type of Induced Decomposition. III Induced Decomposition of Cinnamoyl Peroxide, t-Butyl Peroxycinnamate and t-Butyl 2,3-Diphenylperoxypropionate in Solution
Authors: Ochiai Tameichi , Usuda Yoshitsugu , Yoshida Masayuki , Simamura Osamu
Published: July 2006

Phenyl and benzyl radicals were found to induce decomposition of cinnamoyl peroxide or t-butylperoxycinnamate to give stilbene and 1,3-diphenylpropene, respectively. Similarly, t-butoxyl radicals caused t-butyl 2,3-diphenylperoxypropionate to decompose affording stilbene. A mechanism is proposed which involves a radical atttack on a substrate peroxide producing a radical carrying an odd electron on the carbon atom β to the carboxyl group and its subsequent collapse to final products by way of β-scission.
The Decomposition of t-Butyl erythro- and threo-2,3-Diphenylperoxybutyrate in Solution. The Product Analysis and the Cage Effect
Authors: Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu
Published: July 2006

Decomposition of t-butyl erythro- and threo-2,3-diphenylperoxybutyrate was examined in solution at 60 °C; there was no indication of induced decomposition taking place as is the case with t-butyl 2,3-diphenylperoxypropionate. Various hydrocarbons resulting from the reaction of the 1,2-diphenylpropyl radical in a variety of ways were identified in the product, and t-butyl 1,2-diphenylpropyl ether was found to be formed as cage recombination product in the threo/erythro isomeric ratio which depended on the stereochemistry of the starting peroxybutyrate.
Multifunctional Hydrolytic Catalyses. V. The Reaction of o-Substituted Benzohydroxamic Acids and p-Nitrophenyl Acetate
Authors: Kunitake Toyoki , Okahata Yoshio , Ando Reiko , Hirotsu Sumio
Published: July 2006

Salicylohydroxamic acid(SHA), N-methylsalicylohydroxamic acid(MSHA), and N-methylphthalohydroxamic acid(MPHA) were prepared and their acylation reactions with p-nitrophenyl acetate were studied in aqueous ethanol at 30 °C. Both the acidity and nucleophilicity of the hydroxamic acid group were affected by the functional ortho-substituents(–OH, –COOH). In particular, the undissociated hydroxamic acid group in the MPHA monoanion possessed nucleophilic reactivity. This was brought forth by the general base assistance of the adjacent carboxylate group, as confirmed by the presence of the solvent isotope effect of kH⁄kD=2.5. Only the hydroxamate anion acted as the nucleophile in all other cases.
Dehydroaunulenes. VI. Synthesis and Properties of 1,6,12,17-Tetraphenyl-2,4,13,15-tetrakisdehydro[22]annulene
Authors: Akiyama Shuzo , Nomoto Tateo , Iyoda Masahiko , Nakagawa Masazumi
Published: July 2006

1,6,12,17-Tetraphenyl-2,4,13,15-tetrakisdehydro[22]annulene has been synthesized. The sparlingly soluble tetrakisdehydro[22]annulene was found to be conformationally stable and strongly diatropic.
Spin Trapping of Benzoyloxycyclohexadienyl Radicals by 2,3,5,6-Tetramethylnitrosobenzene (Nitrosodurene) in the Decomposition of Dibenzoyl Peroxide in Benzene
Authors: Suehiro Tadashi , Kamimori Mariko , Sakuragi Hirochika , Yoshida Masayuki , Tokumaru Katsumi
Published: July 2006

The aroyloxycyclohexadienyl radicals (VIII), the key intermediates iates in the homolytic aromatic aroyloxylation, were detected and identified in the decomposition of dibenzoyl peroxide, bis(4-methylbenzoyl) peroxide, and bis(4-methoxybenzoyl) peroxide in benzene-d6 as spin adducts of nitrosodurene.
Reactions of Aroylhydrazones. II. Oxidative Cyclization of Benzil Bis(aroylhydrazones) to Substituted 1,2,3-Triazoles
Authors: Shaban Mohammed A E , Nassr Mahmoud A M
Published: July 2006

Benzil bis(aroylhydrazones) were oxidized with iodine and yellow mercury(II) oxide to 1-(1-α-aroyloxyaryl-ideneamino)-4,5-diphenyl-1,2,3-triazoles. The structure of the prepared compounds was determined by studying their chemical and spectral properties.
Molecular Rearrangements. VII. N-Alkylarylamines (III). Thermal Rearrangement of Secondary Arylamines
Authors: Osman A M , Badr MZA , Abdel-Rahman A E
Published: July 2006

Heating of N-benzyl-o- and p-toluidines resulted in migration of the benzyl group to the corresponding toluidine nucleus. The pyrolysis of N-benzyl-o-toluidine produced ammonia, toluene, bibenzyl, trans-stilbene, o-toluidine together with 4-amino-3-methyldiphenylmethane and 2,3-diphenyl-7-methylindole. N-benzyl-p-toluidine resulted into the same neutral products together with ammonia, p-toluidine, 2,3-diphenyl-5-methylindole together with 2,7-dimethyl-9-phenylacridine. Using phenol or quinoline as solvents, the normal rearranged products were accompanied with 2- and 4-benzylphenols and 2- and 4-benzylquinolines. It was concluded that the pyrolysis of the secondary amines proceeds through their homolytic fission to benzyl and the corresponding toluidino free radicals. Homolysis of some primary products was also observed.
The Preparation of Tetramethylphthalic Anhydride
Authors: Chiba Koji , Endo Eiji , Sakamoto Tokio , Sato Eiji , Fukuhara Ryoichi , Kobayashi Toshiko
Published: July 2006

The alkaline hydrolysis of bis(nitromethyl)prehnitene (1) with aqueous sodium hydroxide gave almost quantitatively disodium tetramethylphthalate (11). Under milder conditions the sodium salts of tetramethylphthalimide (8), N-hydroxytetramethylphthalimide (10), and 2-hydroxy-3-hydroxyimino-4,5,6,7-tetramethylphthalimide (9) were fo were formed, probably as intermediate products of the above reaction. But, pentamethylphenylnitromethane (14) and bis(nitromethyl)isodurene (15) were not hydrolyzed in an aqueous base. From the above results, it is recognized that the sodium nitronate from 1 is unstable in a different way from general nitronates such as the sodium salt of 14 or 15. It appears that the instability of 1 arises from the two adjacent nitromethyl groups on the benzene ring.
Hartree-Fock-Slater Calculations of the ESCA Chemical Shifts for Transition Metal Atoms
Authors: Tatsumi Kazuyuki , Fueno Takayuki
Published: July 2006

Hartree-Fock-Slater calculations have been carried out for inner-shell orbitals of some transition metal atoms (Ni, Rh, and Pt), and the core ionization energies computed by the transition state approximation. It is found that the ionization energy shifts do not conform to the conventional charge-potential approximation; the electron populations in individual valence d and s orbitals need to be considered separately.
Fouling Mechanism in Liquid Phase Oxidation of Carbon Monoxide Catalyzed by Palladium(II) Salts in Acetic Acid Solvents
Authors: Imanaka Toshinobu , Matsumoto Tetsuo , Kimura Toshio , Sakurai Katsumi , Teranishi Shiichiro
Published: July 2006

The fouling mechanism during catalytic activity in the liquid phase oxidation of carbon monoxide has been investigated using catalytic acetic acid solutions containing palladium(II) salts and lithium nitrate as oxidants. The fouling phenomenon becomes understandable upon the recognition that the active palladium catalysts react with the nitrite ion formed during the oxidation reaction to produce inactive-stable complexes.
Molar Volume Equations of Several Molten Binary Systems
Authors: Mochinaga Junichi , Igarashi Kazuo , Kuroda Hideo , Iwasaki Hironori
Published: July 2006

The molar volumes of YCl3–KCl, YCl3–NaCl, YCl3–CaCl2, PrCl3–KCl, PrCl3–NaCl, PrCl3–CaCl2, NdCl3–KCl3 NdCl3–NaCl, and NdCl3–CaCl2 systems in molten state were measured. The results are represented by empirical equations as functions of both temperature and composition. The calculations were carried out by using the methods of least squares and Powell’s procedure.
A New Type of Induced Decomposition. IV. Pyrolysis of t-Butyl Peroxy-3-butenoate in the Gas Phase
Authors: Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu
Published: July 2006

t-Butyl peroxy-3-butenoate decomposes in the gas phase at 115 °C to give carbon dioxide, 1-butene, acetone, 1,5-hexadiene, methane, and ethane. Experiments with iodine, an efficient radical scavenger, indicate the operation of induced decomposition. The mechanism of the formation of 1-butene and 1,5-hexadiene is discussed in terms of a new type of induced decomposition.
Photochemical Conversion of Methoxyketene Intermediate into Methyl Ester in the Photolysis of 2-Methoxy-3-dijphenylmethyl-4-diphenylmethylene-2-cyclobuten-1-one
Authors: Toda Fumio , Todo Yozo , Todo Eishiro
Published: July 2006

The photolysis of methylenecyclobutenone in the presence of benzophenone or oxygen affords the one carbon diminished product, methyl 4,4-diphenyl-2-diphenylmethyl-2,3-butadienoate. The reaction pathway is discussed.
Syntheses of 4-(4-Hydroxy-2,6-dimethylphenyl)-1,2-butanediol and 4-(4-Hydroxy-2,6-dimethylphenyl)-2-butanol.
Authors: Uneyama Kenji , Sakumoto Hironori , Torii Sigeru
Published: July 2006

4-(4-Hydroxy-2,6-dimethylphenyl)-1,2-butanediol (3) and 4-(4-hydroxy-2,6-dimethylphenyl)-2-butanol (4) as precursors for a theaspirone synthesis have been synthesized starting from 3,5-dimethylphenyl methyl ether.
The Heat of Solution and Solvation Number of Lithium Salts in Water–Alcohol Mixtures
Authors: Mashima Michio , Takase Takao , Fukuda Shinroku , Baba Norio
Published: July 2006

The solvation numbers of LiCl and LiI, and of KI for comparison, in water–MeOH mixtures and water–i-PrOH mixtures were determined at an infinite dilution at 25 °C from the adiabatic compressibility. The heats of solution of these salts were also determined. In general, with an increase in the concentration of alcohol the solvation number increases initially to reach a maximum at 10–30 mol% alcohol, then it decreases to a minimum and increases again from about 75 mol% alcohol. The maximum solvation numbers of the salts determined are as follows: LiCl 11.2 mol/mol at 30 mol% MeOH; LiCl 11.5 mol/mol at 15 mol% i-PrOH; LiI 8.2 mol/mol at 12 mol% i-PrOH and KI 14.0 mol/mol at 10 mol% i-PrOH. The larger the cation, the larger the solvation number. Also, the composition of the solvant where the salt containing larger ions has a maximum solvation number has a lower concentration of alcohol. The maximum solvation number of LiI containing a larger anion is smaller than that of LiCl because an iodide ion has a much larger structure-breaking effect than a chloride ion. By the way, there seems to be difference in the structure of the mixed solvent before and after the maximum solvation number.
Characteristics of Coordination Compounds of Calcein Blue for a Tunable Organic Liquid Laser
Authors: Imasaka Totaro , Ogawa Teiichiro , Ishibashi Nobuhiko
Published: July 2006

The lasing and spectroscopic properties of coordination compounds of Calcein Blue with aluminium, calcium, strontium, and barium in water and in a water–ethanol mixture were investigated. The chelate formation improved the lasing properties of Calcein Blue, since the fluorescence quantum yield was increased by the formation of rigid rings in the molecule, and the lasing wavelength could be modified by the metal ion. By using these coordination compounds, tunable laser emissions were observed in the spectral range of 400–478 nm with a low threshold excitation intensity. The threshold excitation intensities excited by the nitrogen laser, the pulse width of which was very short (2.5 ns), were formulated by means of the spectral parameters for such molecules as its Stokes shift was large and its singlet-singlet absorption could be ignored. The calculated values obtained by this formula agreed well with the experimental values in water.
Temperature-independent Delayed Fluorescence of Benzo[f]quinoline in Biphenyl Host: A New Interpretation of Delayed Fluorescence Behavior around 77 K
Authors: Kusumoto Yoshihumi , Gondo Yasuhiko , Kanda Yoshiya
Published: July 2006

The delayed fluorescence observed in the mixed crystals of benzo[f]quinoline in biphenyl host has been found to be independent of temperature in the low temperature region from 90 K down to liquid helium temperature, and subtraction of this temperature-independent contribution from the observed total delayed fluorescence intensity above 90 K has given straight-line fits of the logIDF⁄IP2  vs. 1/T plots, that is, a single activation energy has been obtained over the whole temperature range studied, instead of two different ones as usually assumed. Such a correction has also been given to a new attempt of logIDF  vs. 1/T plots successfully. Moreover, the decay behavior of the delayed luminescence has been studied over the wide temperature and concentration range. It has been concluded that the decay behavior of the temperature-independent delayed fluorescence may mainly be responsible for the nonexponential decay of the delayed fluorescence around 77 K.
Composition and Some Physical Properties of Complex TCNQ Anion Radical Salts Containing Quinolinium, N-Methylquinolinium, and their Isomeric Cations
Authors: Matsunaga Yoshio , Tanaka Tomio
Published: July 2006

Complex TCNQ, anion radical salts containing quinolinium, isoquinolinium, and their methyl derivatives were prepared. Quinolinium and cations having molecular envelopes of 2-methylnaphthalene form 1 : 2 salts, whereas isoquinolinium and cations having molecular envelopes of 1-methylnaphthalene give 2 : 3 salts. Only N-methylquinolinium forms salts containing the solvent of crystallization. The room temperature resistivities of the polycrystalline compactions are in the range from 0.5 to 3.9 ohm cm, and the Seebeck coefficients are in the range from −41 to −54 μV/deg for the 1 : 2 salts and in the range from −12 to −23 μV/deg for the 2 : 3 salts. The diffuse reflection spectra of all the salts are similar to each other. A splitting of the band in the 10×103 cm−1 region was observed only for the 1 : 2 salts. In the total reflectance spectra, the salts show Drude-like edges in the region from 6×103 to 8×103 cm−1.
The Concentration Dependence of the Raman Intensity in Binary Mixtures and the Determination of Polarizability and Hyperpolarizability Derivative Tensors
Authors: Koike Jun , Suzuki Tetsuo , Fujiyama Tsunetake
Published: July 2006

Raman intensities were observed at various concentrations. The observed lines were: the ν8 line of CH3CN (in CCl4 and CH3I), the ν3 line of CH3I (in CCl4), and the ν2 line of CHCl3 (in CCl4). Even after the elimination of the local-field effect, the Raman intensities showed concentration dependencies. The observed solvent effects were explained quantitatively by the use of the dipole interaction model. The polarizability and hyperpolarizability derivatives were determined for the ν8 fundamental of CH3CN. The criteria for the internal standard method were discussed quantitatively.
Crystal Structure and Magnetic Properties of Hydrothermally Synthesized Barium Ferrite, Ba4Fe9O20H6
Authors: Kitahama Katsuki , Kiriyama Ryôiti
Published: July 2006

A new barium ferrite, Ba4Fe9O20H6, has been synthesized by a hydrothermal technique. This crystallizes in a monoclinic system with a=10.263(5), b=5.986(3), c=14.559(6) Å, β=95.20(3)°, Z=2, space group C2/m. The structure was determined by Patterson and Fourier methods from three-dimensional X-ray counter data and refined by block-diagonal least-squares calculations to R=0.098 for 1128 reflections. The structure consists of condensed layers of ferrite anions, Fe(OH)63− clusters, and Ba2+ cations; it has the character of a crystal growth from aqueous solutions. The presence of Fe2+ was confirmed; such ions are located in the condensed ferrite layer. Consequently, the true formula should be written as Ba4[FeIII(OH)6][FeIIFe7IIIO14]. This crystal is ferrimagnetic below the Nèel point of 515 K. The magnetic moment was estimated to be about 10 μB per formula unit at 0 K.
Studies on the Tautomerism of 2-Anilinopyridine and Related Heterocycles
Authors: Takahashi Yoshiyuki , Otsuka Soichi , Masuda Hideyuki , Hirota Minoru , Ito Yoshio , Hamada Yoshiki
Published: July 2006

2-(N-Methylanilino) and 1-methyl-2-phenylimino derivatives of pyridine and quinoline were prepared as models for the amino and the imino tautomers of 2-anilino-pyridine and -quinoline. The ultraviolet, infrared and NMR spectra of these compounds were compared with those of the model compounds. The spectral data show that the amino tautomers are by far preferred in various solvents. The pKa measurement on 1-methyl-2-phenylimino-1,2-dihydropyridine allows the assumption of the tautomeric equilibrium constant.
Synthesis of 4-Amino-2-hydroxybutanoic Acid and Its 3-Methyl Derivative
Authors: Sato Hiroko , Kusumi Takenori , Imaye Kyoto , Kakisawa Hiroshi
Published: July 2006

1,3-Dipolar addition of the nitronic ester (3) to methyl acrylate afforded regiospecifically the isoxzolidine (4), which produced the oxime ether (7) on heating. Reduction of 7 followed by hydrolysis gave the hydroxy amino acid (6), which is known to improve anitibiotic activities. The nitronic ester (3) also reacted regio- and stereospecifically with methyl crotonate to produce the adduct (8). Pyrolysis of (8) followed by reduction and hydrolysis gave the erythro hydroxy amino acid (11).
Retrograde Aldol Reaction of 3-(1-Hydroxy-2,2,2-trichloroethyl)-2,4-pentanedione Catalyzed by the Bivalent Metal Complexes of 2,4-Pentanedione
Authors: Uehara Kaku , Ohashi Yoshiyuki , Tanaka Makoto
Published: July 2006

The bivalent metal complexes of 2,4-pentanedione(M(acac)2) catalyzes the conversion of 3-(1-hydroxy-2,2,2-trichloroethyl)-2,4-pentanedione(A) into chloral and acetylacetone(Hacac) in a chloroform solution. The order of activity of M(acac)2 as the catalyst is: Mg(II), Mn(II)>Co(II)>Ni(II)>Cu(II)<Zn(II). It was found that the catalyzed reaction proceeds through saturation-type kinetics. The Lineweaver-Burk-type plots show linear relationships and are consistent with a mechanism in which a preequilibrium complex formation between M(acac)2 and a substrate is followed by the rate-determining decomposition to give the products. Acetylacetone acts as a competitive inhibitor for the Cu(acac)2-catalyzed reaction. The third stability constant for the Cu–Hacac chelate system can be evaluated from the inhibitor constant as log K3=4.3. The retrograde aldol reactions of 3-(1-hydroxy-2,2,2-trichloroethyl)-5-methyl-2,4-hexanedione and 3-(1-hydroxy-2,2,2-trichloroethyl)-4-phenyl-2,4-butanedione were studied in the same manner as 3-(1-hydroxy-2,2,2-trichloro-ethyl)-2,4-pentanedione. A possible mechanism for the catalysis is proposed.
Preparation of Polyvinylamine by the Hofmann Degradation of Polyacrylamide
Authors: Tanaka Hiroo , Senju Ryoichi
Published: July 2006

Polyvinylamine which contained 95.6 mol% amine units was obtained when the Hofmann degradation was applied to polyacrylamide by use of a very slight excess of sodium hypochlorite and a large excess of sodium hydroxide at 0 to −15 °C for about 15 h. Polyvinylamine hydrochloride (PVAm·HCl) was isolated almost quantitatively as a white powder. PVAm·HCl was freely soluble in water, but insoluble in organic solvents such as methanol, acetone, dioxane, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO). The desalting of PVAm·HCl was performed by passing its aqueous solution through columns of ion exchange resins. The product containing 30.5% nitrogen was obtained in reasonable yield. Polyvinylamine was freely soluble in water, acetic acid, or lower alcohols, but insoluble in solvents such as acetone, dioxane, DMF, and DMSO.
Esters of Phosphorus Oxy Acids as Alkylating Agents. IV. N-Alkylation of Imidazole and Its Analogs with Alkyl Esters of Phosphonic and Phosphinic Acids
Authors: Hayashi Masahiro , Yamauchi Kiyoshi , Kinoshita Masayoshi
Published: July 2006

Methyl, ethyl esters of phosphonic and phosphinic acids were found to be efficient alkylating agents for imidazole, benzimidazole, 1,2,4-triazole, 1,2,3-benzotriazole and pyrazole, giving the corresponding N-methyl or N-ethyl derivatives.
Sound Velocity in Aqueous Solutions of Ammonium Halides
Authors: Endo Harumi , Nomoto Otohiko
Published: July 2006

The sound velocity in water aqueous solutions increases with increasing temperature and reaches the maximum velocity (Vp) at a peak temperature (Tp). In the present paper, the concentration dependence of Tp and Vp in ammonium halides are reported. It was found empirically that the relationship between the hydration number and the slope (ΔTp⁄μ of Tp at infinite dilution for many electrolytes is linear, but that for ammonium halides this is not the case.
Studies with Parchment Supported Membranes. VII. Application of Fick’s Diffusion Law and Nernst-Planck Formulae for Electrical Potential—Consideration of Membrane Field Strength and Energetics of Permeation of Cations
Authors: Siddiqi Fasih A , Beg M Nasim , Haque Abdul , Singh Surendra P
Published: July 2006

Electrolytic transport processes occurring across parchment supported membranes have been described by Nernst-Planck flux equation taking into account the membrane resistance Rm, membrane potential Em  etc.  Em values for various electrolytes display very interesting phenomena. In the case of 1 : 1 electrolyte the Em values are all positive, while in the case of (2 : 1) and (3 : 1) electrolytes surface charge reversal takes place. The diffusion rate sequence and selectivity of the membrane for different uni-, bi-, and tri-valent cations was found to be primarily dependent on the difference in the hydration energies of counter ions in the external solution. On the basis of Eisenman-Sherry theory the diffusion rate sequence of alkali metal cations point towards the weak field strength of the fixed charge groups. Various thermodynamic parameters, ΔH≠, ΔF\eweq, and ΔS\eweq were evaluated by applying the theory of absolute reaction rates to the diffusion process through parchment supported membranes. The values of ΔH\eweq were found to be negative, indicating that diffusion takes place with partial immobilization in the membrane phase. The relative partial immobility was found to increase with increase in the valence of the ions constituting the electrolyte. A formal relation between ΔHhydration, ΔFhydration, and ΔShydration of cations with the corresponding values of ΔH\eweq, ΔF\eweq, and ΔS\eweq for diffusion, was also found to exist for these membranes.
Dielectric Relaxation in Some Substituted Benzaldehydes in Benzene at Different Temperatures
Authors: Singh Buta , Vij J K
Published: July 2006

Measurements of the relative permittivity at 1 MHz and 9.27 GHz, and of the refractive index for the sodium-D line have been made for (A) o-nitrobenzaldehyde, (B) m-nitrobenzaldehyde, (C) m-chlorobenzaldehyde, and (D) p-chlorobenzaldehyde, at 15, 25, 35, and 45 °C in dilute solutions of benzene. The dielectric relaxation times τ(1) and τ(2) have been calculated using the Higasi, Koga, and Nakamura method. The results suggest that the relaxation time for the overall rotation decreases at a greater rate than the one for the internal rotation. The thermodynamic energy parameters have been calculated. The results show that the freedom of rotation of the –CHO group increases around the Calip–Carom bond as an electronegative substituent moves from the o- to m- to p- positions.
Studies on Some Mixed Schiff’s Base Complexes. V.
Authors: Kohli Rakesh Kumar , Bhattacharya P K
Published: July 2006

As regards the preparation and characterization of some new mixed complexes of the type MLL′ where M=Cu(II), Ni(II); L=salicylaldimine and L′=(o-hydroxybenzyl)(ethylideneamine) or o-hydroxydiphenylenethylene-amine or their derivatives, we have carried out the preparation of a few similar types of complexes where L′=2-hydroxy-1-naphthylmethyleneamine. The mixed imine Schiff’s base complexes have been prepared by treating the metal ammine complex with an equivalent amount of salicylaldehyde and 2-hydroxy-1-naphthaldehyde. Amine exchange reactions were also been carried out by treatment of mixed imine Schiff’s base complex with ethylenediamine(en) or propylenediamine(pn). The complexes of new Schiff’s base were formed where diamine have salicylaldehyde condensed at one end and 2-hydroxy-1-naphthaldehyde at the other end. The complexes have been characterized by elemental analysis, TLC analysis, conductance measurements, magnetic measurements, and spectral analysis.
Thermogravimetric Analysis of Tetraalkylammonium Haloborates. I.
Authors: Sheikh S U
Published: July 2006

Thermogravimetric analysis of tetraalkylammonium haloborates lead to the formation of trialkylamine trihaloborane and dialkylamino dihaloborane followed by illpredictable intermediates leading to the formation of boronnitrogen polymers.
Oxidation of Flavanone Hydrazones with Manganese Dioxide
Authors: Sharma T C , Lal Amba , Saksena Vinita
Published: July 2006

Oxidation of flavanone hydrazones(I) with active manganese dioxide gave a mixture of flavanones(II) and the azines(III).
An Application of Current-pulse Electrolysis to an Electro-initiated Polymerization of Acrylamide
Authors: Ogumi Zempachi , Takehara Zenichiro , Yoshizawa Shiro
Published: July 2006

A unidirectional current pulse was applied to the electro-initiated polymerization of acrylamide in a Kolbe system, and the behavior of intermediate was investigated. The formation rate of the oligomer during the current-on pulse was not affected by the pulse length, and it was almost the same as that under steady conditions. An oligomer was also formed during current-off pulse. The formation rate of the oligomer during the current-off pulse was calculated on the base of the mechanism presented in previous papers; the calculated results agreed well with the experimental results. The half-life time of intermediate radical, [RM·], was about 10 ms.
The Microwave Spectrum of Ethyl Isocyanate
Authors: Sakaizumi Takeshi , Yamada Osamu , Ushida Kyoichi , Ohashi Osamu , Yamaguchi Ichiro
Published: July 2006

The microwave spectrum of ethyl isocyanate, CH3CH2NCO, has been obtained in the frequency region from 8.5 to 35.5 GHz. The spectrum identified is attributed to the cis conformation, in which the methyl group eclipses the isocyanato group. The rotational constants in the ground vibrational state obtained are A=14110±3, B=3067.91±0.02, and C=2605.01±0.02 MHz. The dipole moment (μa) for this rotamer is 2.81±0.02 D. Four sets of vibrational satellites were observed and assigned to the transitions in the first, second, third, and fourth excited states of the C–N torsional vibration.