bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reaction of Alkyl Halides with Mercury(II) Salts in Tetrahydrofuran. A Facile Preparation of 4-Alkoxybutyl Acetates and Chlorides
Authors: Watanabe Nanao , Uemura Sakae , Okano Masaya 
Published: July 2006

Abstract
The reaction of primary and secondary alkyl iodides and bromides with Hg(OAc)2 and HgCl2 in tetrahydrofuran (THF) affords the THF-incorporated compounds (1), RO(CH2)4X [X=OAc and Cl, respectively], in good yields. When HgBr2 and aqueous or alcoholic Hg(ClO4)2 were used as mercury(II) salts, the yields of 1(X=Br, OH, and OR′) were low. Similar treatment with HgI2 gave scarcely any 1. A reaction scheme which involves O-alkyltetrahydrofuranium ion as the intermediate is proposed for the formation of 1.
CIDNP Investigation of Aminyl Radicals Formed by Thermolysis of Triazenes
Authors: Albert Klaus , Dangel Karl-Michael , Rieker Anton , Iwamura Hiizu , Imahashi Yuzo 
Published: July 2006

Abstract
Thermolysis of asymmetric triazenes Ar–N=N–NH–R 1 produces anilines Ar–NH2 2, hydrocarbons R–H 3, and N-alkylated anilines Ar–NH–R 4 as the main reaction products. 1H- and 13C-CIDNP experiments show polarization of nuclei in Ar–NH2, Ar–NH–R, R–H and some additional products (especially ring alkylated anilines). These observations are in agreement with the formation of an intermediate radical pair [Ar–NH··R] which must have been formed via homolysis of the tautomeric form ArNH–N=N–R 1′. Temperature-dependent 13C-NMR spectra show a rapid equilibrium between 1 and 1′ at room temperature and above, the tautomeric form 1 being predominant. From the CIDNP spectra the signs of the 1H and 13C hyperfine couplings of aminyl radicals Ar–NH and alkyl radicals R. have been determined.
Photolyses of Ethyl Azidoformate in Cyclic Ethers
Authors: Torimoto Noboru , Shingaki Tadao , Nagai Toshikazu 
Published: July 2006

Abstract
Ethoxycarbonyl nitrene, generated by the photolysis of ethyl azidoformate (I), were inserted preferentially into the α C–H bonds of cyclic ethers. The α C–H bonds of cyclic ethers were much more reactive than the corresponding C–H bonds of hydrocarbons for the insertion of the nitrene. In addition, the reactions in cyclic ethers with an alkyl group at the α-position gave unsaturated alkoxyurethanes via a cleavage of the ring C–O bond. It was found that the nitrene insertion into the α C–H bonds of cis- and trans-2,5-dimethyltetrahydrofurans proceeded non-stereospecifically, while the insertion into the C–H bonds of hydrocarbons proceeded stereospecifically. The formation of the alkoxyurethanes can be explained by a mechanism in which an O–N ylide is included as an intermediate of the nitrene reaction; the non-stereospecific insertion of the nitrene give support to this mechanism.
The Reaction of Arylthallium(III) Compounds with Metal Nitrite. Synthesis of Nitroarenes.
Authors: Uemura Sakae , Toshimitsu Akio , Okano Masaya 
Published: July 2006

Abstract
Arylthallium(III) compounds react smoothly with various metal nitrites such as NaNO2, KNO2, and AgNO2in trifluoroacetic acid to give nitroarenes in good yields. It has been clarified that the reaction proceeds through substitution of thallium moiety by nitroso group at the (ipso) position where thallium was attached previously to aromatic ring to give nitrosoarenes, followed by their oxidation to nitroarenes.
Reaction of Carboxylic Acids with Dioxygen Complexes: A Mechanistic Aspect of the Reaction
Authors: Muto Shigeaki , Kamiya Yoshio 
Published: July 2006

Abstract
The reaction of carboxylic acids with dioxygen complexes MO2(PPh3)2(M=Pt, Pd) at low temperature gives rise to the selective formation of H2O2 and the corresponding dicarboxylato complexes characterized by their physical properties. It is suggested that the reaction can be influenced by either the capability of reactant for coordination to metal center or the stability of resulting metal complex. An equimolar addition of CH2ClCOOH to the dioxygen complexes in the presence of triphenylmethyl bromide at ca. −70 °C gives triphenylmethyl hydroperoxide and the corresponding monocarboxylato complexes in good yields, indicating that the reaction of organic acids with MO2(PPh3)2 proceeds by stepwise mechanism.
Studies in Heterocyclics. VI. Synthesis of Thiazolo-Benzo-Triazepines
Authors: Mahajan M P , Sondhi S M , Ralhan N K 
Published: July 2006

Abstract
2-Imino-3-(o-aminoaryl)-4-thiazolines (II) gave thiazolo-benzotriazepines(I) on condensation with various aliphatic carboxylic acids. Both N-acyl(III) and N,N′-diacyl derivatives(IV) were isolated, and the monoacyl derivatives (III) were also cyclized to thiazolo-benzo-triazepines.
Photochemistry in the Adsorbed Layer. VII. Steric Hindrance in the Type II Cleavage of Adsorbed Alkyl Eetones
Authors: Anpo Masakazu , Kubokawa Yutaka 
Published: July 2006

Abstract
The type I selectivity in the photolysis of adsorbed alkyl ketones is larger for 3-methyl-2-pentanone than for 2-pentanone. Such behavior can be explained by the concept that the type II cleavage is more hindered for the former owing to a steric hindrance arising from the presence of a solid surface.
A Theoretical Analysis of Rotational Isomerism; CNDO/2 Calculations of i-PrSMe, i-PrSEt, i-Pr–S–n-Pr, and (i-Pr)2S
Authors: Ohsaku Masaru , Bingo Norihisa , Eida Kanzo , Murata Hiromu 
Published: July 2006

Abstract
CNDO/2 calculations of i-PrSMe, i-PrS-Et, i-Pr–S–n-Pr, and (i-Pr)2S gave the stable conformations of these molecules and the optimized angles of φ(CSC) of the first three molecules considered.
Reaction Process between Cobalt Tungstate and Chlorine
Authors: Nishihara Hisao , Matsuzaki Ryoko , Saeki Yuzo 
Published: July 2006

Abstract
The reaction between CoWO4 and chlorine proceeds above about 585 °C to form WO2Cl2 and CoCl2. In the presence of carbon, the reaction proceeds above about 345 °C to form CoCl2 and WO3, the WO3 subsequently reacts with chlorine to form WO2Cl2 and WOCl4.
Gamma-Rays Treatment of Odorous Compound in Water
Authors: Irie Setsuko , Kato Norio , Kinoshita Shosaku 
Published: July 2006

Abstract
γ-Rays treatment of earthy odors in public water supplies due to the metabolites in Lake Biwa was studied. The odorous compound was isolated from the metabolites and was identified to be geosmin by the use of gas chromatographmass spectrometer. The effect of additives and competition reaction with p-nitroso-N,N-dimethylaniline revealed that geosmin is decomposed effectively by hydroxyl radical produced by the radiolysis of water.
Apparatus for Thermal Analytic Microscopy and Its Application to Cholesteryl Nonanoate
Authors: Kunihisa Kazuko Sasaki , Hagiwara Seiichi 
Published: July 2006

Abstract
The phase transitions of cholesteryl nonanoate were studied by means of a newly constructed apparatus for thermal analytic microscopy incorporating a thermoelement. It was possible to determine the heat of mesophase transitions more accurately. The transition values of cholesteryl nonanoate on cooling were obtained with the same accuracy as those on heating. The heat of the smectic-solid transition was obtained by slow cooling, which suppressed the supercooling. The vortices caused by cholesteric spherulites, which are similar to those of cholesteryl octanoate, change to circular arrangements of batonnets in the smectic phase. Color changes were observed at the cholesteric-smectic transition in extremely thick specimens. The relations between texture, color, and heat at the cholesteric-smectic transition of cholesteryl nonanoate are discussed.
An Application of H0,max for Estimating the Catalytic Action of Solid Acids and Bases in the Isopropylation of m-Cresol
Authors: Yamanaka Tohr 
Published: July 2006

Abstract
A method of estimating the acid-base property of the active sites in terms of the correlation between the catalytic activities of various solids and their H0,max values is presented. The H0,max denotes an H0 value of the strongest acidic sites and/or conjugate acids of the strongest basic sites. The types of catalytic actions over oxides, hydroxides, a sulfide, sulfates, phosphates, tungstates, and multi-component solid acids in the liquid-phase isopropylation of m-cresol without a solvent were classified into three groups: via a carbonium ion, via a carbanion, and concerted actions. The selectivity for the ortho-isopropylation over every catalyst increased with the increase of H0,max, and this effect of H0,max was explained by the orientation of the adsorbed m-cresol on the catalyst surface.
Catalytic Properties of Metal Sulfates Supported on γ-Al2O3 in the Liquid-Phase Isopropylation of m-Cresol with Propylene
Authors: Yamanaka Tohr 
Published: July 2006

Abstract
γ-Al2O3 was impregnated with various metal sulfates, calcined, and used as catalysts in the liquid-phase isopropylation of m-cresol at 250–300 °C, with the propylene pressure in the range from 15 to 79 kg/cm2. The catalytic activities of the sulfates were in the order: Al2(SO4)3&gt;ZnSO4≈NiSO4&gt;FeSO4&gt;CuSO4&gt;Li2SO4≈ none≈CaSO4&gt;Na2SO4. The order of the selectivity Φ for ortho-isopropylation over para-isopropylation was opposite to that of the catalytic activity. FeSO4/Al2O3 catalysts resulted in the best Φ value and fairly high activity, which were independent of the calcination temperature over the range of 300–500 °C. The formation of Brønsted acidic sites with 1≤H0≤3 as catalytically-active sites was estimated for the FeSO4/Al2O3 and ZnSO4/Al2O3 catalysts.
The Dual Fluorescence Nature of Some N-Monosubstituted Salicylamides
Authors: Kondo Michio 
Published: July 2006

Abstract
Dual fluorescence from N-methylsalicylamide (1) in alcoholic solutions was observed under excitation by 280 nm light, and was ascribed to two different molecular species: one with and the other without intramolecular proton transfer in the lowest excited singlet state. Some related compounds having two identical chromophores showed similar dual emission spectra with weak emission bands at shorter wavelengths. This fact was explained as being due to the intramolecular energy transfer between the two chromophores in the excited state. From the temperature dependence of the intensity ratio of the two emission bands for these compounds, the difference between the activation energies for the two emissive states was estimated.
A Study of trans Influence in Methylmercury(II) Compounds by Means of Vibrational Analysis
Authors: Iwasaki Noriko 
Published: July 2006

Abstract
Force constants K(Hg–C) were evaluated for a series of methylmercury compounds: CH3HgX (X=CH3, F, Cl, Br, I, CN, SCN, As(CH3)3, SCH3, SHgCH3, and S(HgCH3)2). It was found that K(Hg–C) increases in the following order of X: S(HgCH3)2(1.86)&lt;I(2.27)&lt;SCH3(2.33)=CH3(2.330)&lt;As(CH3)3(2.37)≤Br(2.377)≤SHgCH3(2.38)≤Cl(2.382)&lt;SCN(2.39)&lt;F(2.55)&lt;CN(2.61 md/Å). This order coincides, except for the cases of CN and As(CH3)3, with the order of increase in the first ionization potential of X for X=I, SCH3, CH3, Br, Cl, and F. Since this effect of X upon K(Hg–C) is regarded as a vibrational trans influence, this order was compared with that of the coupling constants in NMR, J(199Hg–13C) and J(199Hg–1H), and with the order of the bond-dissociation energy of CH3HgX into ·CH3 and ·HgX.
A Kinetic Study of the Chromium(II) Reduction of Several (Amino acid)pentaamminecobalt(III) Complexes
Authors: Ogino Hiroshi , Tsukahara Keiichi , Tanaka Nobuyuki 
Published: July 2006

Abstract
A kinetic study of the chromium(II) reduction of (O-bonded amino acid)pentaamminecobalt(III) complexes has been carried out in acid solutions. The second-order rate constants in M−1 s−1 (1 M=1 mol dm−3) at 25 °C and I=1.0 M (NaClO4) for α-alanine, phenylalanine, α-aminoisobutyric acid, β-alanine, β-aminobutyric acid, γ-aminobutyric acid, and ε-aminohexanoic acid complexes are 1.8×10−2, 1.5×10−2, 2.4×10−3, 7.5×10−2, 5.0×10−2, 1.22×10−1, and 1.49×10−1 respectively. The values of ΔH\eweq lie in the range of 6.4–7.7 kcal mol−1 (1 cal=4.184 J), and those of ΔS\eweq, in the range of −42–−37 cal K−1 mol−1, except for the α-aminoisobutyric acid complex, the ΔH\eweq and ΔS\eweq values of which are 11.4 kcal mol−1 and −32 cal K−1 mol−1 respectively. The role of the amino acid ligands in the inner-sphere electron-transfer reactions is discussed.
Oxidation of Acetaldehyde Catalyzed by Cobalt(II) Tetraphenylporphyrin
Authors: Tezuka Meguru , Sekiguchi Osamu , Ohkatsu Yasukazu , Osa Tetuo 
Published: July 2006

Abstract
Cobalt(II) tetraphenylporphyrins catalyzed the autoxidation of acetaldehyde giving peracetic acid quantitatively. The p-substituents of phenyl groups of tetraphenylporphyrin influenced the catalytic activity, cobalt(II) tetra(p-methylphenyl)porphyrin being remarkably active. The effect of the base added into the reaction system was such that an appropriate quantity of the base gave rise to a maximum rate of oxidation. The rate equation was determined experimentally. From the results of kinetics and ESR study, it was concluded that an oxygen molecule activated through the electron transfer from a cobalt(II) ion abstracted the hydrogen of acetaldehyde to initiate the autoxidation.
The Association Constants of Hexaamminechromium(III) and Tris(ethylenediamine)chromium(III) Ions with Several Univalent Anions in Aqueous Solutions
Authors: Takahashi Tatsuo , Koiso Takefumi 
Published: July 2006

Abstract
The thermodynamic ion-association constants of hexaamminechromium(III) and tris(ethylenediamine)chromium(III) with several univalent anions were determined in aqueous solutions at 25.0 °C. The logKcon values obtained by the conductometric method are 1.37 for [Cr(NH3)6]3+–Cl−, 1.58 for [Cr(en)3]3+-Cl−, 1.57 for [Cr(NH3)6]3+–Br−, 1.50 for [Cr(en)3]3+–Br−, 1.53 for [Cr(NH3)6]3+–NO3−, and 1.49 for [Cr(en)3]3+–NO3−. The log KSP values obtained by the spectrophotometric method are 1.65 for [Cr(en)3]3+–Cl−, 1.46 for [Cr(en)3]3+–Br−, and 0.90 for [Cr(en)3]3+–ClO4−; the value for [Cr(en)3]3+–ClO4− could be indirectly calculated from the apparent ion-association constant of [Cr(en)3]3+–Br− determined in the solutions containing both bromide and perchlorate ions. Though the detailed comparison of the ion-association constants obtained in this study was limited, it could be concluded that the Kcon values were in relatively good agreement with the Ksp values obtained on the given ion-pairs and that the ion-association constants of chromium(III) complex cations with several univalent anions are slightly less than those of the corresponding cobalt(III) complex cations with their anions.
The Photochemical Reaction of 1,2-Naphthoquinones with Aldehydes. II. The Photo-addition Reactions of Aliphatic Aldehydes to 1,2-Naphthoquinones
Authors: Takuwa Akio 
Published: July 2006

Abstract
3-Acyl-1,2-naphthalenediols and 1,2-naphthalenediol monoacyl esters were obtained from the photochemical reactions of 1,2-naphthoquinones with aliphatic aldehydes. 3-Halogeno-1,2-naphthoquinones gave the corresponding 1,2-naphthalenediol monoacyl esters, 3-acyl-1,2-naphthalenediols, which are the same products as those from the photochemical reactions of 1,2-naphthoquinone with those aldehydes and 3-halogeno-4-acyl-1,2-naphtoquinone when they were irradiated in aldehydes. 3-Methyl-1,2-naphthoquinone, however, gave the corresponding 1,2-naphthalenediol monoacetate and 3-methyl-4-acetyl- 1,2-naphthoquinone when it was irradiated in acetaldehyde. These photochemical reactions were applicable for syntheses of 3-acyl-1,2-naphthalenediols and 1,2-naphthalenediol monoacyl esters.
Doubly Charged Ion Mass Spectra of Monosubstituted Aromatic Compounds
Authors: Sakurai Hiroshi , Tatematsu Akira , Nakata Hisao 
Published: July 2006

Abstract
The 2E doubly charged ion mass spectra of twelve simple monosubstituted aromatic compounds were recorded. The spectral pattern of these compounds can be classified into three types. When the substituent is strongly electron-donating such as the amino or dimethylamino group, a very intense molecular ion peak appears, no fragment ion peak being observed. Phenol, anisole, toluene, and chlorobenzene show both molecular and fragment ion peaks in varying intensities. The parent benzene itself behaves similarly. Only fragment ion peaks were observed for nitrobenzene and aromatic carbonyl compounds such as benzaldehyde, acetophenone, methyl benzoate, or benzoic acid. The major fragmentation reactions are discussed.
Catalytic Dehydration of Ethers on Nickel Oxide–Silica–Alumina
Authors: Imai Hisao 
Published: July 2006

Abstract
The dehydration of diethyl ether was studied on synthetic nickel oxide–silica–alumina catalysts in the temperature range of 340–400 °C and at pressures less than 50 Torr. It was found that ethylene, butenes, water, and small amounts of carbon monoxide and methane were formed on the catalysts of lower nickel content. The rate constant for the formation of butenes showd a maximum on the catalyst of 10 atom% nickel. The mechanism of the formation of the butenes was discussed by studying the catalytic dehydration of various ethers.
The Photoreaction of Pyrazine Derivatives
Authors: Yamada Kazutoshi , Katsuura Kiyoshi , Kasimura Hideaki , Iida Hirotada 
Published: July 2006

Abstract
The irradiation of the pyrazine derivative with an α-carbonyl substituent (1) under a nitrogen atmosphere gave hydroxypyrazine (2) and two solvent adducts (3 and 4). In the case of 1e, the charge-transfer complex of pyrazine and dihydropyrazine, produced by the reduction of the pyrazine, was isolated. The mechanism of this photoreaction was similar to that of flavine. The attack of oxygen on dihydropyrazine produced 2. Furthermore, the photoreduction with DTT occurred through the intermediate, which was similar to the case of flavine. The reaction rates of various pyrazines were measured. The quenching studies indicate that the photoreaction proceeds via the n-π* triplet state.
The Reaction of Disodium Tetracarbonylferrate(–II) with Carboxylic Esters and Carbothioic Esters
Authors: Watanabe Yoshihisa , Yamashita Masakazu , Igami Mineo , Mitsudo Take-aki , Takegami Yoshinobu 
Published: July 2006

Abstract
The reaction of carboxylic and carbothioic esters with disodium tetracarbonylferrate has been studied. Aryl and thiolic esters reacted with the ferrate under mild conditions to give aldehydes after the reaction mixture had been quenched with acetic acid, but alkyl esters did not. 3-Benzylidenephthalide and phthalide gave 2-phenyl-1,3-indanedione and a dimeric product respectively.
Studies of Enamines. VIII. Reactions of Enamino Ketones with Benzoyl and Thiobenzoyl Isocyanates
Authors: Tsuge Otohiko , Inaba Akitaka 
Published: July 2006

Abstract
The reaction of enamino ketone 1, derived from acetylacetone, with benzoyl isocyanate (4) gave the isomeric benzoylcarbamoyl derivatives 6 and 9, and/or 2-pyridone 7, depending upon the reaction conditions. Similarly, enamino ketone 2, derived from benzoylacetone, reacted with 4 to afford the isomeric benzoylcarbamoyl compounds 12, 13, and/or 2-pyrone 14. It has been found that the carbamoyl compound 12 was thermally converted into 13 and 14. Enamino ketones 1 and 2 reacted with thiobenzoyl isocyanate (5) at room temperature to yield the 2-pyridones 7 and 15, respectively. On the other hand, enamino ketones 3, derived from benzoylacetaldehyde and secondary amines, reacted with 4 to give the corresponding 2-benzoylcarbamoyl-2-penten-2-one compound 18, while in the reaction with 5, 3 gave the 1,3-thiazin-4-one 19 and/or (4+2) cycloaddut 20.
Nitration of Binary and Ternary Schiff Base Complexes of Cu(II)
Authors: Thaker B T , Bhattagharya P K 
Published: July 2006

Abstract
Nitration of the coordinated ligands in the complexes bis[1-(2-hydroxyphenyl)ethylideneamine or its methyl derivative]Cu(II) and N,N′-ethylene or propylene bis[1-(2-hydroxyphenyl)ethylideneaminato]Cu(II) have been carried out. Similar nitration reactions of mixed diamine Schiff base complexes of Cu(II) have also been carried out. The substitution products have been characterized by elemental analyses, comparison with authentic samples in case of binary complexes and by means of magnetic moments, electronic and IR spectral studies. The orientation of incoming substituents in the chelates is found to be the same as that in uncomplexed 2-hydroxyacetophenone or methyl substituted 2-hydroxyacetophenone. Nitration reactions in case of mixed ligand complexes confirm the structure.
Studies with Parchment Supported Membranes. VIII. Determination of the Thermodynamic Effective Fixed Charge Density of Barium Phosphate Membrane by Various Methods and Evaluation of Permselectivity
Authors: Siddiqi Fasih A , Beg M Nasim , Singh Surendra P , Haque Abdul 
Published: July 2006

Abstract
The thermodynamic effective fixed charge density, the most important parameter governing transport phenomena in membranes, was estimated by methods of TMS, Altug and Hair and the most recent one of Kobatake based on the thermodynamics of irreversible processes. Kobatake’s equation has also been utilized for the evaluation of permselectivity of membranes. The two limiting forms of his equation for dilute and concentrated ranges gave identical values of θ (charge density) for barium phosphate membrane. The theoretical predictions for membrane potential by the equation were borne out quite satisfactorily by experimental results obtained with the investigated membranes.
A Study of Self Oscillatory Chemical Reaction of Gallic Acid and Potassium Bromate System
Authors: Babu J Sreekantha , Bokadia M M , Srinivasulu K 
Published: July 2006

Abstract
The oscillatory phenomenon during oxidation of gallic acid with potassium bromate, catalyzed by cerium ion in acid medium with stirring was investigated. The cross section of a three dimensional graph for the regions where the oscillatory behavior can be observed is given. Effect of Ag+and Br− on the oscillatory behavior was studied.
Some New β-Diketone Complexes of Ruthenium(III) with Triphenylphosphine and Triphenylarsine
Authors: Natarajan K , Agarwala Umesh 
Published: July 2006

Abstract
The syntheses of some new β-diketone complexes of Ru(III) with triphenylphosphine and triphenylarsine have been described. Their spectral (IR and visible) and magnetic properties have been reported. Some of them show unusual magnetic moment.
Cathodic Reduction of Nitrobenzene on the Packed-bed Copper Electrode
Authors: Yoshizawa Shiro , Takehara Zenichiro , Ogumi Zempachi , Tsuji Toshio 
Published: July 2006

Abstract
An application of a packed-bed copper electrode to the formation of aniline by the cathodic reduction of nitrobenzene was investigated. As the particles for the packed-bed, spherical particles of an anion exchange resin chemically plated with copper were successfully used. Though the current efficiency for the aniline formation on the packed-bed electrode in a batch cell decreased with continuing electrolysis, the efficiency was improved by the electrolysis under a flowing electrolyte and became very high, i.e., near 100%. This is due to the removal of the accumulated products on the electrode surface by the flowing electrolyte. The effective depth of the bed electrode on which the nitrobenzene reacted cathodically was also determined from the measurement of the potential profile in a packed-bed electrode: the result was about 3 mm. This low value of the effective depth is ascribed to the low conductivity of the electrolyte and to the high electronic conductivity of the packed-bed. This may be improved by using bed particles of lower electronic conductivity and a higher cell capacity may be expected.