bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Intramolecular Participation of Sulfide Linkage on the Reactivity of Carbenes and Diazoalkanes. II. Alkylcarbenes and Diazoalkanes Bearing Arylthio and Allylthio Groups on β-Carbon
Authors: Kondo Kiyosi , Ojima Iwao 
Published: July 2006

Abstract
β-Arylthio- and β-allylthioalkylcarbenes were generated from the corresponding ketones by a modification of the Bamford-Stevens method. Chemical evidence for the formation of novel cyclic ylides, i.e., thietanonium ylides, by an intramolecular electrophilic addition of the carbene to the sulfur atom was obtained. The resulting ylides underwent various types of rearrangements to afford cyclopropyl sulfides, thiaazulenes, thietanes, and/or tetrahydrothiophenes. The mechanisms and the relative amounts of the transition energies for these rearrangements are discussed. An intramolecular cycloaddition of β-allyl- and β-crotylthioalkyldiazoalkanes is also described. The final products of the reaction were 3-thiabicyclo[4.1.0]heptanes. A thiabicyclic pyrazoline, which is presumed to be an intermediate of the cycloaddition, could be isolated in the case of the thermal decomposition of 4-allylthio-4-methylpentan-2-one tosylhydrazone.
The Reduction of Enamines with Carbonylhydridoferrates
Authors: Mitsudo Take-aki , Watanabe Yoshihisa , Tanaka Masato , Atsuta Shoji , Yamamoto Kazuo , Takegami Yoshinobu 
Published: July 2006

Abstract
Enamines react with an alcoholic solution of [FeH(CO)4]− (1), [Fe2H(CO)8]− (2), and [Fe3H(CO)11]− (3), with the absorption of carbon monoxide at room temperature, to give the corresponding saturated tertiary amines. The reduction of the pyrrolidine enamine of 2-methylcyclohexanone with 1, 2, and 3 gave cis and trans N-(2-methyl-1-cyclohexyl)pyrrolidine. The cis/trans ratio of the products were characteristic of 1, 2, and 3; the values, 0.67, 1.2, and 2.1 respectively, represent the bulkiness of the hydrides. The mechanism of the reduction was discussed.
Synthetic Studies on Phosphorylating Reagent. IV. A Novel Synthesis of Nucleoside-3′,5′ Cyclic Phosphates by the Use of 2-(N,N-Dimethylamino)-4-nitrophenyl Phosphate
Authors: Taguchi Yoshihiko , Mushika Yoshitaka 
Published: July 2006

Abstract
A novel method for the synthesis of nucleoside-3′,5′ cyclic phosphate has been investigated. The intermediates, nucleoside-5′ 2-(N,N-dimethylamino)-4-nitrophenyl phosphates (3a–d), were prepared in good yields by the condensation of unprotected nucleosides with 2-(N,N-dimethylamino)-4-nitrophenyl phosphate (2), using dicyclohexylcarbodiimide (DCC) in dimethylformamide (DMF). Treatment of the intermediates 3a–d with acetic acid in boiling pyridine under high dilution condition gave nucleoside-3′,5′ cyclic phosphates in fairly good yields and small amount of other nucleotides, whereas nucleoside-2′,3′ cyclic phosphate was obtained by the reaction in DMF at 100 °C. An attempt at the direct synthesis of the cyclic nucleotide by refluxing the reaction mixture of unprotected nucleoside with DCC and 2 in pyridine was also successful to afford the similar results as in the stepwise procedure.
A Macrocyclic Enzyme Model System. Substrate Specificity for the Inclusion into Paracyclophane Oxime and the Subsequent Acyl Transfer Reaction
Authors: Murakami Yukito , Sunamoto Junzo , Okamoto Hiroshi , Kawanami Kiyomiki 
Published: July 2006

Abstract
In order to characterize the intrinsic nature of 10-hydroxy-11-hydroxyimino[20]paracyclophane (Oxime-I) as being an enzyme model, the acylation reactions of Oxime-I with p-nitrophenyl carboxylates have been investigated in an alkaline aqueous acetone. The usual saturation-type kinetics has been observed for the reactions of p-nitrophenyl decanoate (PNPD), laurate (PNPL), and palmitate (PNPP) with Oxime-I. The acyl transfer reaction was consistent with the following two sequences: (la) pre-equilibrium formation of the inclusion complex between Oxime-I and a substrate, (lb) pre-equilibrium acid dissociation of the inclusion complex, and (lc) rate-determining acyl transfer from a substrate to Oximate-I in the inclusion state; and (2a) pre-equilibrium acid dissociation of Oxime-I, (2b) pre-equilibrium formation of the inclusion complex between Oximate-I and a substrate, and (2c) rate-determining acyl transfer from a substrate to Oximate-I in the inclusion state. On the basis of the compensation correlation between enthalpy and entropy for binding process, the inclusion of a long chain carboxylate into the cavity of Oxime-I is controlled by entropy. It is interesting to note that the binding constants for the present inclusion complexes are considerably larger (K\simeq104–105 M−1) than those for the complexes formed between phenyl esters or azo dyes and cycloamyloses (K\simeq102–103 M−1). Thus, the paracyclophane skeleton provides an effective binding site due to the hydrophobic cavity. Since the most stable inclusion complex was formed with PNPD, the inclusion of the present esters may be not exclusively due to the hydrophobicity provided by an apolar hydrocarbon tail, but significantly due to the molecular geometry or bulkiness characterized by the folded ester molecule. This effect approves the presence of substrate specificity due to the molecular geometry for Oxime-I. In reference to the activation parameters, the acyl transfer process is controlled by entropy in a manner similar to the alkaline hydrolysis in the bulk phase and the complex formation as well. PNPP is least stabilized in the binding process due to the most unfavorable entropy effect, whereas most favorably deacylated in the acyl transfer due to the entropy factor. Consequently, the net change in the free energy is largely reflected on the entropy term. The deceleration effect observed in the reaction of PNPD with Oxime-I at a higher acetone content and the kinetic behavior of alkaline hydrolysis of the three carboxylate esters have also been discussed.
Autoxidation of Toluic Acids Catalyzed by Cobalt and Bromide Ions in Acetic Acid
Authors: Kamiya Yoshio , Ushiba Toshisuke 
Published: July 2006

Abstract
The effect of toluic acid concentration on the rate of autoxidation of toluic acids catalyzed by cobalt acetate and sodium bromide was elucidated. p-Toluic acid has shown a similar reactivity against oxidation to m-toluic acid, but a much different one from o-toluic acid. Although the rate of oxidation of p-toluic acid at 0.023 M cobalt increased with increasing p-toluic acid concentration and appeared to reach a limiting value, it was of first order with respect to the substrate concentration over wide range of concentration in the presence of 0.058 M cobalt. While, the rate of oxidation of o-toluic acid has shown higher values than the other toluic acids at substrate concentrations below 1.5 M and a maximum value at substrate concentration 0.75 M, suggesting that o-toluic acid can be oxidized easily but retards the catalysis by cobalt bromide. It was found that benzenecarboxylic acids remarkably retard the catalysis by cobalt and bromide ions, and the rate of oxidation of toluic acids is higher than that of toluene at such a low substrate concentrations as 0.34 M. The ease of oxidation of toluic acids can be attributed to the smaller rate constant of termination of carboxy benzyl peroxy radicals according to the polar and steric effects.
Carbon-Carbon Bond Formation by Selective Coupling of Alkylthioallylcopper Reagent with Allylic Halides
Authors: Oshima Koichiro , Yamamoto Hisashi , Nozaki Hitosi 
Published: July 2006

Abstract
The reaction of 1-alkylthioallylcopper reagents with allylic halides affords the SN2′ type substitution product in excellent yield. The more synthetically useful reagent, 1,3-bis(methylthio)allylcopper reagent behaves in the same fashion. Attempts to hydrolyze the vinyl sulfide moiety to an aldehyde unit is successful only in the latter case. Yomogi alcohol is synthesized stereospecifically in the light of these results.
Steric Requirements in Base-Promoted Elimination Reactions
Authors: Ishizawa Akio 
Published: July 2006

Abstract
The effect of the steric requirement of the attacking base in base-promoted elimination reactions was studied using a variety of pairs of diastereoisomeric bases. The pairs of diastereoisomeric alkoxide bases examined gave difinitely different cis-olefin to trans-olefin ratios from elimination reactions of secondary alkyl bromides and tosylates in dimethyl sulfoxide. The results indicate unambiguously that the steric requirement of the attacking base is an important controlling factor in determining the olefinic product distribution in these elimination reactions. The structural effect of the solvent molecule was also investigated using pairs of diastereoisomeric alcohols in base-promoted elimination reactions. Under a variety of conditions the effect upon the product distribution observed was rather small, as compared with those observed for the diastereoisomeric bases, to be an important contributing factor on the product distribution.
Role of Chlorine in β-FeOOH on Its Thermal Change and Reactivity to Sulfur Dioxide
Authors: Ishikawa Tatsuo , Inouye Katsuya 
Published: July 2006

Abstract
The state of Cl in β-ferric oxide hydroxide (β-FeOOH) was examined by X-ray diffraction, IR absorption, chemical analysis, DTA, and TGA. The adsorption of SO2 was determined as a measure of the surface activity. No influence of Cl contained in the crystal appeared in the X-ray diffraction patterns and surface area. The absorption bands at 640 and 840 cm−1 in IR spectra showing the deformation vibration of OH group diminished with the decrease of Cl content. It was shown that the path for β-FeOOH to transform into α-Fe2O3 by heating differentiates from the sample including more than 11.5% Cl/Fe to one including less than 11.5% Cl/Fe. This critical Cl content is equal to the amount of Cl when Cl fills up the characteristic tunnels existing in the β-FeOOH crystal. Cl in β-FeOOH interferes both its transformation into α-Fe2O3 and the recrystallization of resultant α-Fe2O3. These effects were explained by the stabilization of the β-FeOOH structure by Cl in tunnels and the bonding between Cl and Fe. The amount of chemisorbed SO2 was lowered by Cl which was adsorbed on outer surfaces.
Lanthanide-Induced Nuclear Magnetic Resonance Shifts and Molecular Structure of l-Azetidine-2-Carboxylic Acid. II. Determination of Molecular Conformation
Authors: Inagaki Fuyuhiko , Takahashi Seizo , Tasumi Mitsuo , Miyazawa Tatsuo 
Published: July 2006

Abstract
Lanthanide-induced shifts (LIS) in 1H NMR spectra of l-azetidine-2-carboxylic acid were observed in D2O solution using Pr(III), Nd(III), and Eu(III) nitrates as shift reagents. By taking the LIS of one of the protons as reference, the shift ratios for the other four protons were calculated. The shifts ratio obtained were nearly constant for the three lanthanide ions, except for that with respect to the α proton which is located closest to the lanthanide ion. This indicates that the contribution of the contact shift is appreciable only for the observed LIS of the α proton and is negligible for the LIS’s of the β and γ protons. The constancy of shift ratios assures, in addition, that the magnetic tensor is axially symmetric. Therefore, the LIS’s of the β and γ protons may be used for the structure determination. For the β and γ protons, the ratios of LIS’s intrinsic to the lanthanide-substrate 1:1 complex were corrected for the contribution of diamagnetic shifts due to complex formation which were estimated by the use of La(III) nitrate. The line broadening induced by Gd(III) was also observed. The structure analysis based on these data shows that the four-membered ring of l-azetidine-2-carboxylic acid is puckered with the dihedral angle of 25° and the carboxylate is in the equatorial position.
Metal(II)-Ion Promoted Hydrolysis of Glycylglycine
Authors: Nakata Toshio , Tasumi Mitsuo , Miyazawa Tatsuo 
Published: July 2006

Abstract
The hydrolysis of glycylglycine was studied in the presence of Cu(II) and Zn(II) at various pH values between 3.4 and 6.3. Glycine produced by the hydrolysis and remaining glycylglycine were trimethylsilylated and their relative quantities were determined by gas-liquid chromatography. The reaction is promoted by both metal ions. In the presence of Cu(II) the pH-rate profile has a maximum at pH ca. 4.4, whereas in the presence of Zn(II) the rate increases as pH becomes higher. These kinetic results are discussed in terms of the structures of metal(II)-glycylglycine complexes in aqueous solution.
The Thermal Changes in Gels of the SiO2–Al2O3–In2O3–H2O System
Authors: Kasai Mitsuhiro , Kudo Yoshiyuki , Hamada Shuichi 
Published: July 2006

Abstract
The synthesized coprecipitated gels in the SiO2–Al2O3-In2O3n-π*–H2O system showed an allophane-like pattern in the DTA except for the indium-rich gels. The exothermic peak temperature in the DTA was lowered from 980 to 940 °C with an increase in the indium content, while that on mixed gels was scarcely lowered at all. A new small exothermic peak around 880 °C in the DTA was observed in the coprecipitated gels with more than 11.93 wt% of In2O3; it was considered to be due to the structural change in the gels which arose from the formation of the indium (III) oxide. The firing products of the coprecipitated gels were identified as mullite, indium (III) oxide, and indium (III) silicate. The mullite formed in the coprecipitated gels included indium ions at 900 °C, accompanied by an increase in its unit cell volume, while the indium ions were almost entirely removed from the mullite lattice at 1200 °C.
The Structures and Thermal Behaviors of Bivalent Metal Succinates in the Solid State
Authors: Nagase Kenzo , Yokobayashi Hiroko , Muraishi Kazuo , Sone Kozo 
Published: July 2006

Abstract
The relations between the structures and thermal behaviors of the succinates of Mg(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) were studied. In the case of the copper salt, the dehydration of its dihydrate began easily at room temperature. However, the tetrahydrates of Mg, Co, and Ni held their waters more tightly, and changed from crystalline to amorphous state in the course of dehydration which began at 50–60 °C. The anhydrous salts of Mg and Co recrystallized at 306 and 272 °C, respectively, with a sharp exotherm on each DTA curve. The cobalt salt showed stepwise color changes, pink \xrightarrowdehydration bluish violet \xrightarrowrecrystalllzation pink. PbC4H4O4 exhibited a phase transition from tetragonal to cubic at 160 °C with ΔH=2.5 kJ/mol and ΔS=5.9 J/deg·mol. The phase transition was reversible and seems to be accompanied with a conformational change of the succinate ion.
The Radical Formation of Polyethylene by Tesla Discharge
Authors: Yokohata Akira , Harakon Katsuyuki , Takimoto Kazuto , Tsuda Satoru 
Published: July 2006

Abstract
The ESR spectra of polyethylene discharged by a Tesla coil in an atmosphere of various gases were observed. An alkyl radical showing a six-line spectrum was formed in the Tesla discharge at 77 K, whereas a polyenyl radical was mainly produced by the discharge with an increase in the duration time; these facts showed that the effects of the Tesla discharge were similar to the γ-irradiation up to a high dose.
Group Interactions in Polyelectrolytes. IX. The Amination Kinetics of Chloromethylated Polystyrene in Binary Mixed Solvents
Authors: Kawabe Hiroshi 
Published: July 2006

Abstract
All the aminations of chloromethylated polystyrene (CMPS) and benzyl chloride with i- and s-butylamine in N,N-dimethylformamide (DMF), in dioxane, and in DMF-dioxane mixtures conformed to the ordinary second-order kinetics. The activation parameters in the pure solvents revealed that the much higher amination rate in DMF than in dioxane was due to both the lower value of ΔH\eweq and the higher value of ΔS\eweq in DMF. The rate of amination in DMF–dioxane was investigated as a function of the composition of the mixed solvent. The observed rate constants in DMF–dioxane mixtures fell substantially on the curves calculated on the basis of Kondo and Tokura’s theory concerning reaction rates in binary mixed solvents. It is suggested in this paper that the higher rate of amination in DMF is due to the strong solvation of the activation complex in DMF to form an addition product, and that it is also due to the relative increase in the configurational entropy of the reaction system at the transition state from dioxane to DMF.
A Study on Anode Effect in KF–2HF System. I. ESCA Spectra of Carbon and Graphite Anode Surfaces
Authors: Imoto Hiroki , Nakajima Tsuyoshi , Watanabe Nobuatsu 
Published: July 2006

Abstract
The ESCA spectra of carbon and graphite electrodes, used as an anode in the molten KF–2HF system at 100 °C, indicated that a (CF)n film was formed on the surface of the electrodes. This may give strong support to the assumption that the anode effect in molten KF–2HF is caused by the formation of (CF)n on the carbon and graphite electrodes.
A Semi-empirical Calculation of the Substituent Effect on the 1H Chemical Shift of Benzene
Authors: Niwa Jun 
Published: July 2006

Abstract
The applicability of a semi-empirical expression for obtaining the relative 1H chemical shifts in substituted aromatic side-chains, which was presented in the preceeding paper (J. Niwa, This Bulletin, 48, 118 (1975)), has been examined for ring protons of monosubstituted benzenes.
An ESR Study of Diborane Anion Radicals in the Adsorbed State
Authors: Sogabe Kunihisa , Hasegawa Akinori , Miura Masaji 
Published: July 2006

Abstract
The ESR spectra were examined for diborane anion radicals, B2H6−, formed when diborane adsorbed on several kinds of adsorbents was irradiated with γ-rays at 77 K or diborane adsorbed at 77 K on adsorbents pre-irradiated with γ-rays at 77 K. The radicals in the adsorbed state were compared with those in an argon matrix, previously reported.
The Back-extraction Behavior of Chelate Compounds. II. Some Aspects of the Secondary Dithizonate of Copper
Authors: Honjo Takaharu , Unemoto Toshiyuki , Kiba Toshiyasu 
Published: July 2006

Abstract
The behavior of secondary copper dithizonate in carbon tetrachloride, chloroform, 1,2-dichloroethane, benzene, monochlorobenzene, o-dichlorobenzene, and nitrobenzene has been investigated by a kinetic study of the back-extraction of the copper ion in order to clarify the extraction mechanism and to ascertain the chemical form of this chelate.
The Reaction of Acetylenecarboxylic Acid with Amines. XVII. The Addition of Dialkyl Acetylenedicarboxylates to Several Carcinogens
Authors: Iwanami Yasuo 
Published: July 2006

Abstract
Hazardous carcinogens, α-naphthylamine (I), benzidine (II), 2′,3-dimethyl-4-aminoazobenzene (o-aminoazotoluene) (III), 2-amino-l-naphthol (IV), and 4-methylaminoazobenzene (V), easily reacted with esters of acetylenedicarboxylic acid (VI and VII) to give addition products, whose carcinogenicity could possibly be changed.
The Photolysis of α-Haloketones. II. The Intramolecular Reactions of 9-α-Bromopropionylanthracene
Authors: Matsumoto Tamotsu , Sato Masanori , Hirayama Satoshi 
Published: July 2006

Abstract
The main photolysis products of 9-α-bromopropionylanthracene were identified as 2-methyl-1-aceanthrenone and 9-vinylanthryl ketone. The yield of 9-bromoanthracene was very small. A significant solvent and temperature dependence was noted on the yields of these products. The photolysis at −196 °C resulted in the formation of almost 100% of 9-vinylanthryl ketone.
The Catalytic Hydrogenolysis of Alkyl-substituted Aziridines
Authors: Sugi Yoshihiro , Nagata Mitsuru , Mitsui Sekio 
Published: July 2006

Abstract
Alkyl-substituted aziridines were hydrogenolysed, mainly at the less-substituted C–N bonds over Raney Ni, to yield β-amines. This hydrogenolysis occurred with the retention of the configuration. The differences in behavior between aziridines and oxiranes may be ascribed to the difference in polarisation between C–N and C–O bonds in the transition state of the hydrogenolysis.
The Reaction of N-Hydroxylamino Compounds with Triphenylphosphine and CCl4
Authors: Ohashi Takehisa , Appel Rolf 
Published: July 2006

Abstract
In the reaction of triphenylphosphine with N-p-toluene-N-hydroxylamine and CCl4, p-azotoluene and p-azoxytoluene were formed as the main products. On the other hand, in the reaction using N-p-toluenesulfonyl-N-hydroxylamine, sulfonyliminophosphorane was obtained.
Photochemical Reactions of 3,3-Bis(dialkylamino)acrylophenones and 3-Dibenzylaminopropiolophenone
Authors: Aoyama Hiromu , Hasegawa Tadashi , Nishio Takehiko , Omote Yoshimori 
Published: July 2006

Abstract
The photolysis of 3,3-bis(dialkylamino)acrylophenones 1a, b, and c gave the 3a, b, and c pyrroles respectively. 3-Dibenzylaminopropiolophenone (2) reacted with water upon irradiation to give N,N-dibenzylbenzoylacetamide (5), whereas the addition of acetic acid to 2 proceeded without irradiation.
Lactone Carboxylic Acids. IX. Base-Catalyzed Rearrangement of Ethyl α-Hydroxyaminoaconate Leading to the Formation of Isoxazolines
Authors: Torii Sigeru , Ukida Masasi , Tanaka Hideo 
Published: July 2006

Abstract
The syntheses of 4-ethoxycarbonyl-3-methoxycarbonyl-5,5-pentamethylene-Δ2-isoxazoline (2b) and its 4-hydroxy and 4-acetoxy derivatives (3a and 3b) by the base-catalyzed rearrangement of ethyl γ,γ-pentamethylene-α-hydroxyaminoaconate (1) were described.
A New Synthesis of Pyrimido[4,5-e][1,2,4]triazines from 5,5-Dibromopyrimidines
Authors: Sugimoto Takashi , Matsuura Sadao 
Published: July 2006

Abstract
A new method for the synthesis of pyrimido-[4,5-e][1,2,4]triazines from 5,5-dibromopyrimidines was studied. Condensation of dibromopyrimidines (1a, b) with aminoguanidine or its analogues gave the 6,8-dioxo series (5) of the pyrimidotriazine, and aminodibromopyrimidines (2a, b) gave the 6-amino-8-oxo series (6).
The Dipole Moments and Conformations of cis-2-Styrylfurans and cis-2-Styrylthiophenes
Authors: Gruttadauria Salvatore , Pappalardo Giuseppe C , Scarlata Giuseppe , Torre Michele 
Published: July 2006

Abstract
Electric dipole moments at 25 °C in benzene have been measured for cis-2-styrylfurans and -styrylthiophenes which are chloro- and nitro-substituted in 2′-, 3′-, 4′-position. Results of dipole moment analyses in conjunction with UV spectroscopic data have been discussed in terms of preferred conformations for these compounds.
The Effect of the Hydrostatic Pressure on the Hydrogen-bond Formation between Phenol and Dioxane in Hexane
Authors: Suzuki Keizo , Tsuchiya Masao 
Published: July 2006

Abstract
The near-UV absorption spectra of phenol-dioxane in n-hexane were observed under hydrostatic pressures up to 1480 atm and at 30 °C. With an increase in the pressure, the spectra shift toward the longer wavelength side and the amount of the hydrogen-bonded phenol increases. The equilibrium constant for (Remark: Graphics omitted.) was obtained, and the volume change accompanying the hydrogen-bond formation was estimated to be −3.0–−3.4 cm3/mol.
Enthalpies of Combustion of Organic Compounds. I. 8-Quinolinol
Authors: Sakiyama Minoru , Nakano Toshiro , Seki Syûzô 
Published: July 2006

Abstract
A rotating-oxygen-combustion bomb calorimeter equipped with a platinum lined bomb has been constructed and calibrated. The enthalpy of combustion of 8-quinolinol(c) was determined. Thermodynamic quantities obtained are as follows: ΔEc°=−4458.90±1.60, ΔHc°=−4460.76±1.60 and ΔHf°=−81.24±2.00 kJ mol−1 for the crystalline state and ΔHf°=27.6±2.6 kJ mol−1 for the gaseous state.
Isotropic Rayleigh Light Scattering in Two-component Systems. The Interdependence of the Concentration and the Density Scattering
Authors: Shiokawa Yoshinobu , Suzuki Shin 
Published: July 2006

Abstract
The isotropic Rayleigh ratios in two-component systems are discussed in terms of the fluctuation of the thermodynamic quantities. It is found that the isotropic Rayleigh ratio, Ris, is the sum of the concentration scattering, Rc, due to fluctuation of the concentration and the so-called density scattering, Rd:
R_is=R_c+R_d
Thus, the cross-term of the concentration scattering and the density scattering, suggested by Bullough, is not included in the above expression. Our conclusion is confirmed by the determination of the molecular weight of sucrose.