bluuebunny/crossref_metadata_2025_split huggingface dataset:
Polarized Absorption Spectra of TCNNQ-Aromatic Hydrocarbon Molecular Complexes
Authors: I’haya Yasumasa J , Yunoki Toru , Suzuki Noboru 
Published: July 2006

Abstract
Polarized absorption spectra of TCNNQ and TCNNQ-anthracene, pyrene, phenanthrene (Group 1), 1,2-benzanthracene, chrysene and triphenylene (Group 2) molecular complexes were measured in the frequency range of 13.5–42 kK at room temperature and 80°K. The mole ratio of donor to acceptor was found to be 2 : 1 for Group 1 complexes and 1 : 1 for Group 2 complexes. Two broad bands observed in each spectrum of these complexes were assigned to be the first and the second charge-transfer (CT) bands. The CT bands were enhanced in intensity and displaced to the red at 80°K. The first CT bands were confirmed to be associated with the charge transfer from the highest occupied molecular orbital (HOMO) of donor to the lowest vacant molecular orbital (LVMO) of acceptor. The charge transfer mechanism for the second CT bands may be divided into two classes; for Group 1 complexes it is mainly due to the second LVMO of acceptor, while for Group 2 complexes, in addition to this, there is a possibility of the charge transfer from the second HOMO of donor to the LVMO of acceptor.
The Polarized Absorption Spectra of Some α-Aminoanthraquinones
Authors: Inoue Hiroyasu , Hoshi Toshihiko , Yoshino Junko , Tanizaki Yoshie 
Published: July 2006

Abstract
The π–π* electronic absorption spectra of 1-amino-, 1,4-diamino-, and 1,4,5,8-tetraaminoanthraquinones were investigated by means of the polarized absorption spectra using stretched PVA sheets and theoretical calculations. Each of these compounds has four absorption bands in the near-ultraviolet region (210–340 nm) and one in the visible region. The bands of the aminoanthraquinones which appear in the visible region can be assigned to the intramolecular charge-transfer transitions associated with the charge migration from the ami no group to the carbonyl groups.
Symmetry Rule for Predicting Bond Distortions in Conjugated Hydrocarbons
Authors: Nakajima Takeshi , Toyota Azumao , Fujii Sadao 
Published: July 2006

Abstract
A symmetry rule for predicting molecular shapes which is based on the second-order Jahn-Teller effect has been applied to the predictions of bond distortions in a number of nonalternant hydrocarbons in their ground and electronically excited states. In spite of the very crude approximation that only the lowest-lying excited state plays a dominant role in determining the energetically most favorable nuclear displacement, a fairly clear-cut criterion for molecular-symmetry reduction was obtained. The actual types of the most soft bond distortions, determined by examining the two-center components of transition densities, are in good agreement with the results of variable bond-length SCF MO calculations and available experimental results. The problem of symmetry reductions possible in large cyclic polyenes C4n+2H4n+2 is briefly discussed.
Interaction of 1,2-Dichloroethane with Benzene and other Aromatic Hydrocarbons
Authors: Morita Akio , Takahashi Hiroaki , Higasi Keniti 
Published: July 2006

Abstract
Experiments to confirm Kubo’s conclusion on the complex formation of 1,2-dichloroethane with benzene were carried out following his procedure. Dielectric measurements were carried out with inert solvents hexane and cyclohexane. The interactions between 1,2-dichloroethane and each of the compounds toluene and p-xylene were also studied with inert solvents hexane, cyclohexane, and carbon tetrachloride. The results are discussed in relation to complex formation.
Radiolysis of Mixtures of Hydrocarbons and Ammonia. I. Formation of Ethylamine from a Mixture of Ethylene and Ammonia
Authors: Tokunaga Okihiro , Hamanoue Kumao , Okamoto Jiro , Danno Akibumi 
Published: July 2006

Abstract
The γ-radiolysis of a gaseous mixture of ethylene and ammonia has been investigated over the whole range of composition. The products of decomposition were primarily hydrogen, ethane, n-butane, ethylamine, and acetylene. It was observed that the yields of ethane, n-butane, and ethylamine increased with the increasing concentration of ammonia, and that the G-values of these products at 98 mol% ammonia were 0.52, 2.12, and 0.89, respectively. Addition of oxygen or nitric oxide as radical scavengers tended to reduce the yields remarkably. The G-value of ethyl radical was calculated from the G-values of ethane, n-butane, and ethylamine, and the limiting value of G(C2H5·) was determined by extrapolation to 100 mol% ammonia. The value thus obtained agrees with the initial G-value of hydrogen radical, i.e., GH=7.0±0.6, which was obtained by Eyre and Smithies in the study of the γ-radiolysis of ammonia gas. From these results, it was concluded that thermal hydrogen radicals produced by the γ-radiolysis react quickly with ethylene, giving ethane, n-butane, and ethylamine from ethyl radicals.
Preparation and Properties of Iron(II) Complexes with Tetraoxime Analogues
Authors: Bagkes Joseph , Masuda Isao , Shinra Koichiro 
Published: July 2006

Abstract
Three polymeric iron(II)-tetraoxime chelates of the formula CH3C(NOH)C(NOH)-R-C(NOH)C(NOH)-CH3, where R: C6H4-O-C6H4, C6H4-C6H4, and 2,6-pyridyl, are characterized and compared with monomeric α-dioxime analogues. Analytical data indicate that in the solid state these Fe-N4 type chelates do not coordinate an axial base. Axial substitution takes place only upon dissolution into pyridine or similar basic solvents. The resemblance between the substituted polymer chelates and the monomeric dimethylglyoxime compounds, as far as their electronic spectra are concerned, is discussed. While the solid state polymers are all paramagnetic with moments 2.0–2.5 B.M., ESR data show that in solution a conversion into a diamagnetic species takes place. A strong absorption band due to the O–N stretching vibration appears at about 1650 cm−1 upon complexing of the nitrogen atoms. The paramagnetism and the reflectance spectra of the solid state samples are related to their structure.
Kinetic Studies of the Electron-Transfer Reaction in Iron(II) and Iron(III) Systems. V. The Reaction in Mixed Solvents of Methanol and Water
Authors: Wada Goro , Endo Akiko 
Published: July 2006

Abstract
The electron-transfer reaction between Fe(II) and Fe(III) species in mixed solvents of methanol and water was investigated by the use of Fe-59 as the radioactive tracer. The hydrolysis constant of Fe3+, KH, in the mixed solvent decreases gradually as the mole faction of methanol, xM, increases. At very high acidities, ionic association between Fe3+ and ClO4− ions occurs, thus forming an ion-pair in the mixed solvent. The apparent rate constant, kapp, of the electron-transfer reaction is a function with respect to xM; kapp does not vary much in the concentration range xM≤0.3, but it decreases as xM grows higher than 0.3. kapp is also dependent upon [H+] and in a linear relationship with [H+]−1. Thus, the two reaction paths, Fe2+-Fe3+ (k0) and Fe2+-FeOH2+ (kH), are deduced to be prevailing. Both rate constants, k0 and kH, decrease with an increase in xM. The constancy of kapp at 0≤xM≤0.3 is a result of compensation between the increasing KH value and the decreasing k0 and kH values. By taking into account the values of ΔHH\eweq=7.6 kcal/mol and ΔSH\eweq=−19.1 e.u. at xM=0.2, both of which do not differ greatly from those in pure water, the reaction is concluded to proceed through the hydrogen-atom-transfer mechanism in the mixed solvent, the inhibiting effect of methanol being due to the reduction of the hydrogen bondings between water molecules.
The Reaction Mechanism of 2-Dimethoxymethyl-3-methoxypropionitrile with Acetamidine. I. A Revised Structure of the Intermediate
Authors: Nishino Takenori , Kiyokawa Masumi , Miichi Yoshiyuki , Tokuyama Kanji 
Published: July 2006

Abstract
The reaction of 2-dimethoxymethyl-3-methoxypropionitrile (1) with acetamidine yields 2,7-dimethyl-5,6-dihydropyrimido[4,5-d]pyrimidine (6) via an intermediate, λmaxMeOH 262 mμ. This intermediate has been identified as 2-acetamidinomethylene-3-methoxypropionitrile (5) without being isolated. However, this assignment seems to be somewhat inconsistent with the stabilities of an acetal group in basic media and with the UV spectra of compounds with structures similar to 5. The reaction of 1 with sodium methoxide gave a dimeric compound (8). This result suggests the formation of 2-dimethoxymethylacrylonitrile (2) in the initial stage of the reaction of 1 with acetamidine. The reaction of acrylonitrlie with acetamidine yielded 2-methyl-4-amino-5,6-dihydropyrimidine (23), whose UV spectrum in methanol showed its absorption maximum at 270 mμ in neutral media and at 258 mμ in basic media. Therefore, the structure of the intermediate may be concluded to be 2-methyl-4-amino-5-dimethoxymethyl-5,6-dihydropyrimidine (27) instead of 5, and the reaction may be concluded to proceed via the pathway of 1→2→27→6.
Synthesis of 5,5-Dimethyl-4-acetoxy-2-cyclopentenone, an Intermediate in the Total Synthesis of Illudin M, through Sulfur Compounds. A Novel Intramolecular Migration of Ethylenedioxy Group
Authors: Matsumoto Takeshi , Shirahama Haruhisa , Ichihara Akitami , Shin Hyonsobb , Kagawa Shohei 
Published: July 2006

Abstract
5,5-Dimethyl-4-acetoxy-2-cyclopentenone, an intermediate in the total synthesis of illudin M, has been prepared from 1-methylsulfinyl-3,3-dimethyl-4,4-ethylenedioxy-2-pentanone as well as from 1,1 -trimethylenedithio-3,3-dimethyl-4,4-ethylenedioxy-2-pentanone. An example of new intramolecular transketalization has been described.
Olefin Disproportionation by Rhenium, Tungsten, and Molybdenum Based Catalysts. Effect of the Addition of Oxygen
Authors: Uchida Yasuzo , Hidai Masanobu , Tatsumi Takashi 
Published: July 2006

Abstract
ReCl5 was activated with Et3Al and oxygen to give a catalyst effective for the disproportionation of α-olefins as well as internal olefins. The catalyst species was deactivated by excess oxygen. The catalyst system consisting of either WCl6 or MoCl5 and Et3Al exhibited disproportionation activity in a short range of Al/M (M=W or Mo) molar ratio. The activity decreased with the increase in the Al/M ratio, but was restored by the introduction of oxygen.
Stereochemical Studies and Synthetic Applications of Bis-β-keto Sulfoxides
Authors: Yamamoto Yasusi , Nozaki Hitosi 
Published: July 2006

Abstract
Bis-β-keto sulfoxides of the MeSOCH2CO(CH2)nCOCH2SOMe (n=7, 8, or 10) type are prepared. The dl and meso isomers are isolated, and the stereochemistry of bis-β-keto sulfoxides (n=8) is established by means of the asymmetric synthesis of the resolvable isomer from an optically-active ester, (−)-menthyl–O–CO(CH2)8–CO–O–(−)-menthyl, and methylsulfinylcarbanion. It is concluded that the higher-melting one is the meso isomer and that the lower-melting one is racemic. The condensation of bis-β-keto sulfoxides, MeSOCH2CO(CH2)8-COCH2SOMe, and allyl bromide in the presence of a base and the subsequent desulfurization give the olefinic ketone, (CH2=CHCH2CH2CO(CH2)4)2. Optically active sulfoxide, MeSOCH2COPh, is obtained from (−)-menthyl benzoate and methylsulfinylcarbanion.
The Preparation and Deamination of 1-t-Butyl-3-amino-, 1-t-Butyl-3-aminomethyl-, and 1-t-Butyl-2-aminomethylazetidine
Authors: Chen Teng-Yueh , Hung Mu-Huang , Chen Po-Tau , Ohta Masaki 
Published: July 2006

Abstract
1-t-Butyl-3-amino, 1-t-butyl-3-aminomethyl-, and 1-t-butyl-2-aminomethylazetidine were prepared by the ammonolysis of 1-t-butyl-3-azetidinyl tosylate, and by the reduction of 1-t-butyl-3-cyano, and 1-t-butyl-2-cyanoazetidine respectively. In the deamination, both of the first two azetidines gave only the corresponding alcohols, 1-t-butyl-3-azetidinol and 1-t-butyl-3-hydroxymethylazetidine, while the last one was found to afford two products, 1-t-butyl-2-hydroxymethylazetidine and 1-t-butyl-3-hydroxypyrrolidine. The deamination products were identified as the corresponding acetates.
The Substituent Effect. II. Normal Substituent Constants for Polynuclear Aryls from the Hydrolysis of Arylcarbinyl Benzoates
Authors: Sawada Masami , Tsuno Yuho , Yukawa Yasuhide 
Published: July 2006

Abstract
The rates of the alkaline hydrolysis of 9 polynuclear arylcarbinyl benzoates were measured in 70% (v/v) aqueous acetone at 25°C. The new set of σ0 values for polynuclear aryls was obtained, using the ρm value established by the hydrolysis of m- and p-substituted-benzyl benzoates. In the present reaction, it is possible to assume that the peri-hydrogen steric effect is practically absent, bacause o-tolyl derivative gives a σ0 a value comparable with that of p-tolyl, and 1-naphthyl with that of 2-naphthyl. The set thus obtained can be successfully described in terms of two components; self-atom polarizability and Streitwieser’s inductive index, ∑rij−1.
The Base-catalyzed Condensation of α-Haloaldehydes with Dichloroacetates
Authors: Takeda Akira , Tsuboi Sadao , Wada Satoshi , Kato Hiroshi 
Published: July 2006

Abstract
The reaction of aliphatic α-haloaldehydes with methyl dichloroacetate in the presence of sodium methoxide was carried out. α-Chloroaldehydes afforded 2,4-dichloro-2,3-epoxyalkanoates (5), whereas α-bromoaldehydes gave 2,2-dichloro-3,4-epoxyalkanoate (7). The attempted epoxy-carbonyl rearrangement of 5 with hydrogen chloride or thionyl chloride failed. The thermal decomposition of methyl 2,4-dichloro-2,3-epoxynonanoate (5c) at 300–400°C afforded methyl 3-chloro-2-oxo-3-nonenoate (9c), and the similar treatment of methyl 2,4-dichloro-4-methyl-2,3-epoxypentanoate (5a) afforded a mixture of methyl 3,4-dichloro-4-methyl-2-oxopentanoate (6a), methyl 3-chloro-4-methyl-2-oxo-3-pentenoate (9a), and methyl 3-chloro-4-methyl-2-oxo-4-pentenoate (10). The treatment of 5 with thiourea in methanol gave the thiazole derivative (15), but neither sodiomalonate nor sodioacetoacetate reacted with 5.
The Accelerated Reaction of 2,2-Diphenyl-1-picrylhydrazyl with Cupric 3-(1-Butenyl)-2,4-pentanedionate in Frozen Solutions and Its ESR Spectra
Authors: Uehara Kaku , Kamei Kiyohiro , Tanaka Makoto , Murata Niro 
Published: July 2006

Abstract
The rate enhancements upon freezing in the reaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with cupric 3-(1-butenyl)-2,4-pentanedionate (3-α-butenylacetylacetonate) were studied in benzene, dioxane, and cyclohexane. It was observed that the degree of the rate enhancements in frozen solutions varied remarkably with the kind of solvent. The order of the accelerating effect was as follows: benzene&gt;dioxane&gt;cyclohexane. Upon freezing, the hyperfine structure in the ESR spectra of DPPH collapsed into a single line, but the peak-to-peak line width (ΔHpp) changed appreciably with the solvents used. The order of the values of ΔHpp was as follows: cyclohexane&gt;dioxane&gt;benzene. These results suggest that the enhancement of the rate in a frozen solution is due to the increased concentration of reactants in the liquid region existing among the crystalline solvents.
Ionic Decomposition of Phenylazotriphenylmethane in Trifluoroacetic Acid
Authors: Kamigata Nobumasa , Kobayashi Michio , Minato Hiroshi 
Published: July 2006

Abstract
Acid-catalyzed decomposition of phenylazotriphenylmethane was studied in mixtures of benzene and large excess concentration of trifluoroacetic acid. The decomposition was of first order and the rate was much faster than that in pure aromatic solvents. The values of activation energy (Ea=22.3 kcal/mol) and activation entropy (ΔS\eweq=−5.2 e.u) fit the isokinetic relationship established for the ionic decomposition of benzenediazonium tetrafluoroborate in aprotic polar solvents and of phenylazo p-tolyl sulfone in mixtures of benzene and trifluoroacetic acid. The reaction products were benzene, biphenyl, benzophenone, triphenylmethane, triphenylmethyl alcohol and nitrogen. Orientations and partial rate factors for the phenylation of monosubstituted benzenes indicated that not phenyl radical but phenyl cation was produced as an intermediate. Further, the UV spectrum of PAT in benzene and trifluoroacetic acid shows λmax at 403 mμ (logε 4.48) and λmax at 427 mμ (logε 4.48). However, the UV spectrum of PAT in benzene and in the absence of trifluoroacetic acid has no absorption in this range. The formation of triphenylmethyl alcohol and the UV spectra of PAT in acid solution indicate that triphenylmethyl cation was formed as an intermediate. A plausible mechanism was discussed.
Electrochemical Fluorination of N-Nitrosodiethylamine
Authors: Watanabe Nobuatsu , Haruta Masatake , Chang Byongte 
Published: July 2006

Abstract
The fluorination of (C2H5)2N–NO at a nickel anode under a variety of operating conditions resulted in the formation of liquid products such as (CF3)2C2F5N, (C2F5)2CF3N, (C2F5)3N, and the compounds containing C–N groups together with gaseous fragmentation products such as CF4, C2F6, CHF3, NF3, and N2. Current efficiency of total gaseous products increased appreciably as the concentration of substrate and current density became higher. Effect of electrolysis temperature was so characteristic as observed in the fluorination of triethylamine that there existed the temperature at which a maximum value of current efficiency was given. On the basis of both the experimental results on the effects of operating conditions and the electrochemical measurements in hydrogen fluoride solutions of Et2N–NO, mechanism of the fluorination reaction was discussed and compared with those of diethylamine and triethylamine.
Bromination of Aliphatic Ketones with Copper(II) Bromide in Organic Solvents. I. The Reaction of Acetone with Copper(II) Bromide in Methanol
Authors: Kojima Yoshitane , Kawaguchi Shinichi 
Published: July 2006

Abstract
The reaction between acetone and methanol to form acetone dimethylacetal attains equilibrium quickly under the influence of copper(II) bromide. Reaction of both acetone and acetone dimethylacetal with copper(II) bromide thus proceed simultaneously to produce copper(I) bromide, hydrogen bromide, and brominated substrates. The mass balances of these reactions were established. On account of the retarding effect of copper(I) bromide and the enhancing effect of hydrogen bromide, the time course of reaction is too complicated to be analyzed, and the initial rate formula was determined. Two reaction pathways were suggested and copper(II) bromide was considered to play dual roles as a catalyst and a brominating agent in either case. The acid catalyzed reactions were also found to follow a two-term rate law, one being independent of and the other first order with respect to copper(II) bromide.
Radiolyses of Mixtures of Ammonia and Hydrocarbons. II. Formation of Hydrogen from Mixtures of Ammonia and Olefins (Ethylene, Propylene and Butadiene)
Authors: Hamanoue Kumao , Okamoto Jiro , Tokunaga Okihiro , Danko Akibumi 
Published: July 2006

Abstract
γ-radiolyses of gaseous mixtures of ammonia and olefins (ethylene, propylene and butadiene) have been investigated over the whole composition range of mixtures, and consideration was given on the primary processes of hydrogen formation. From the extrapolated values of G(H2) obtained in the γ-radiolyses of the mixture of ammonia and olefins, it was found that the non-scavengeable G(H2) of ammonia, ethylene, propylene and butadiene were 0.68–0.72, 1.26, 1.06, and 0.33, respectively. Gas-phase radiolyses of ammonia-perdeuterated olefin mixtures have also been investigated. From kinetic calculation on the data of isotopic mixtures of hydrogen, the following results were obtained; 1) both thermal and non-scavengeable hydrogen molecules are produced by the γ-radiolysis of ammonia, and the non-scavengeable hydrogen molecules are produced for the most part by a unimolecular process, 2) almost all the hydrogen molecules produced by the γ-radiolyses of olefins (ethylene, propylene, and butadiene) are non-scavengeable; a unimolecular process plays an important role in the case of ethylene, and in other cases a bimolecular process. G(H2) of the butadiene radiolysis is very small compared with that of other olefins and with the calculated value of butadiene, i.e., G(H2)&lt;1. The discrepancies can be interpreted in terms of the addition reaction of the “hot” hydrogen radicals to butadiene to form t-2-butene.
The Amine Sensitization of the Fluorescence of Tris-(dibenzoylmethano)europium(III)
Authors: Fukuzawa Tadashi , Ebara Nozomu 
Published: July 2006

Abstract
The effect of amines on the efficiency of fluorescence of tris(dibenzoylmethano)europium(III) has been investigated in a methanol solution. Amines with low pKb values seem to form 1 : 1 complexes with the chelate, and the change in the fluorescence intensity of the chelate is due exclusively to the formation of a complex, which fluoresces more strongly than the chelate itself. It seems that the sensitization of the fluorescence is due to the change in the relaxation lifetime. In the case of amines with aromatic moieties, sensitization through energy transfer may also take place, but this never occurs unless the amine molecule is present in the complex. The structure of the complex and the mechanism of sensitization are discussed.
Acidity and Acid Strength of Zeolite Catalysts
Authors: Ikemoto Misako , Tsutsumi Kazuo , Takahashi Hiroshi 
Published: July 2006

Abstract
The influence of pretreatment temperature, silica-to-alumina mole ratio, the kind of cation and degree of cation exchange on the number of acid sites, and the acid strength of zeolite catalysts were examined by means of amine titration. Strong acid sites whose H0 function is lower than −8.2 were analyzed by ultraviolet spectroscopy. Though H-zeolites have fairly strong acid sites (−10.8&lt;H0&lt;−8.2), the number of acid sites decreases with the decrease of the silica-to-alumina mole ratio, as a result of the collapse of the zeolite structure. Ca-zeolites have an acid site distribution similar to that of H-zeolites only when the silica-to-alumina mole ratio is larger than 4.6. Only La-form Y-zeolite has strong acid sites (H0&lt;−10.8). When the degree of La-exchange exceeds 85 mol%, zeolite shows an acid coloration even with dinitrotoluene with pKa−12.8.
A Theoretical Consideration of the Electron-scavenging Process In Liquid Hydrocarbons. III. Integral Transforms of the Distribution Functions
Authors: Yamazaki Hideo , Shinsaka Kyoji 
Published: July 2006

Abstract
The relations of integral transforms between various distribution functions are discussed using the potential control approximation ignoring the diffusion term in the Smoluchowski equation; the initial spatial distribution of the electron-ion pair or the initial distribution of electrons from the central ion core in a spur, χ(r, 0); the relative G-value of electron recombination, G(ksCs) as a function of the concentration of the scavenger and the rate constant; the time dependence of the electron concentration, N(t), after pulse irradiation; and the relaxation time spectrum, K(n), of the decay of the electron concentration after pulse irradiation or of the weight function, K(n), in the initial exponential distribution of thermalized electrons in a spur are shown to be connected by the square diagram of Laplace transforms:
(Remark: Graphics omitted.)
By the use of this relation, the various distribution functions are evaluated from the empirical formulas of G(ksCs) proposed by Schuler et al. and by Hummel.