bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structure and Reactivity of Small Ring Compounds. I. Solvolyses of Spiro[2,4]hept-4-yl and Spiro[2,5]oct-4-yl 3,5-Dinitrobenzoates
Authors: Tsuji Takashi , Moritani Ichiro , Nishida Shinya 
Published: July 2006

Abstract
The solvolyses of spiro[2,4]hept-4-yl, spiro[2,5]oct-4-yl,2-methylenecyclopentyl, 2-methylenecyclohexyl, 2,2-dimethylcyclopentyl, and 2,2-dimethylcyclohexyl 3,5-dinitrobenzoates have been examined in 60 wt% aqueous dioxane. The solvolysis rate of spiro[2,4]hept-4-yl 3,5-dinitrobenzoate was 850 times greater than that of the corresponding allyl derivative, the 2-methylenecyclopentyl ester, and 3.0×105 times greater than that of the 2,2-dimethylcyclopentyl ester. Similarly, in the cyclohexyl series, spiro[2,5]oct-4-yl 3,5-dinitrobenzoate solvolyzed 330 times faster than the 2-methylenecyclohexyl ester and 1.9×105 times faster than the 2,2-dimethylcyclohexyl ester. In a buffered solution, the spiro[2,4]heptyl ester gave a mixture of spiro[2,4]heptan-4-ol (46%), bicyclo[3,2,0]heptan-1-ol (28%), and 3-methylenecyclohexanol (10%), besides internally-returned 3,5-dinitrobenzoate of bicyclo[3,2,0]heptan-1-ol (12%). Under the same conditions, the spiro[2,5]oct-4-yl ester produced spiro[2,5]octan-4-ol (71%), bicyclo[4,2,0]octan-1-ol (21%), and 3,5-dinitrobenzoate of bicyclo[4,2,0]octan-1-ol (6%), the product of internal return. The implication of these results are discussed.
Stable Biscarbodiimides
Authors: Iwakura Yoshio , Noguchi Kohji 
Published: July 2006

Abstract
The dehydrosulfurization of bisthioureas containing at least one aromatic residue results in the corresponding biscarbodiimides. Biscarbodiimides with bulky groups, such as t-butyl and 2,6-xylyl, can be isolated without any polymerization and disproportionation; the steric hindrance of the bulky groups makes such isolation possible. Polymerization and disproportionation interrupt the isolation of biscarbodiimides with less bulky groups. Despite their nonpolymerizability, they give rise to the other known addition reaction of aromatic carbodiimides.
Oxidation of Phenyl Radical by Copper(II) Complexes in Acetic Acid and in Acetonitrile
Authors: Wada Keisuke , Yamashita Junzo , Hashimoto Harukichi 
Published: July 2006

Abstract
The reactions between the phenyl radical and copper(II) complexes in acetic acid and in acetonitrile were investigated. It was found that the phenyl radical produced from the thermal decomposition of benzoyl peroxide in acetic acid is oxidized by the copper(II) ion to give a considerable amount of phenyl acetate. With cupric propionate, chloride, and bromide, “ligand-transfer” products, i.e., phenyl propionate, chloro-, and bromobenzene, respectively, were also obtained. In addition, a larger yield of the oxidation product was obtained from a 1 : 1 complex than from a 1 : 3 complex of copper(II)-phenanthroline. These facts, together with the results on solvent effects, can be successfully explained on the basis of a ligand-transfer mechanism rather than an electron-transfer mechanism. The effects of substituents of benzoyl peroxide on the reaction were an electron-transfer mechanism. The effects of substituents of benzoyl peroxide on the reaction were so small that one cannot decide whether the ligand-transfer mechanism is a radical or an ionic one. Some abnormalities were observed in the reaction with cupric acetylacetonate. Additionally, the reaction with cuprous chloride was examined, and the behavior of the copper(I) ion in the reaction discussed.
Studies of Aminosugars. XVII. Production of 3-Amino-3-deoxy-d-glucose by Bacillus Species
Authors: Umezawa Sumio , Umino Kimio , Shibahara Seiji , Omoto Shoji 
Published: July 2006

Abstract
3-Amino-3-deoxy-d-glucose was isolated from a fermentation broth of a Bacillus species designated as Bacillus aminoglucosidicus. This demonstrated for the first time the presence of a monosaccharide aminodeoxypyranose in nature. The aminosugar was isolated in a high yield by using column chromatography with cation exchange resin. The identity of the product with 3-amino-3-deoxy-d-glucose was completely established by comparing the natural product and its derivatives with synthetic 3-amino-3-deoxy-d-glucose and its corresponding derivatives in elemental analyses, infrared spectra and mixed melting point determination.
A Theory of the Electronic Structures and Spectra of Negative Ions
Authors: Tsubomura Hiroshi , Sunakawa Sigenobu 
Published: July 2006

Abstract
Some aromatic anions in solutions show absorption spectra with many sharp bands in the visible and ultraviolet regions. It is pointed out that this is rather remarkable in view of the fact that aromatic molecules have very small electron affinities, nearly zero or even negative, in the gas phase. It is then emphasized that the potential for the electron in the negative ions is much more localized than the Coulomb potential. Accordingly, some of the features of the negative ions are deduced by the use of a simple well-type potential. The important conclusions obtained are: 1) Negative ions may have discrete electronic energy levels not only in the E≤0 region but also in the E&gt;0 region, that is, higher than the detachment energy. 2) The larger the domain of the potential well for the electron, the discrete energy levels can exist at the higher energy. 3) These energy levels at E&gt;0 should, of course, be unstable, mostly leading rapidly to the electron detachment, but their lifetime are the longer, the larger the domain of the potential well. These consequences seem to account well for the above-mentioned spectra of aromatic anions. Other features of the negative ions and the nature of the charge-transfer states in the charge-transfer complexes are also discussed.
Phosphorescence Bands of Quinones and α-Diketones
Authors: Kuboyama Akira , Yabe Sanae 
Published: July 2006

Abstract
Phosphorescence bands, their life times, and the excitation spectra of anthraquinone, α-naphthoquinone, phenanthrenequinone, acenaphthenequinone, benzophenone, benzil, furil, and camphorquinone at 77°K in a rigid solution and in the crystalline state have been studied. In a rigid solution the lifetimes of these phosphorescence bands are in the range (10–0.1 msec). The solvent effect on lifetimes shows clear differences between o- and p-quinones. The behavior of these phosphorescence bands is similar to that of the n→π* bands of these compounds. From these facts, these bands are all safely identified as π*→n bands. The phosphorescence bands of p-quinones in the crystalline state are at far longer wavelengths than those in a rigid solution, and the lifetimes of the former are far longer than those of the latter. The dichroism of excitation spectrum of the phosphorescence band of anthraquinone proved that the phosphorescence band is polarized perpendicularly to the 320 mμ band and parallel to the 270 mμ band.
Photochemical Reaction between Acridine and Acridan in the Presence and in the Absence of Oxygen. II. Studies by the Flash Technique
Authors: Kira Akira , Koizumi Masao 
Published: July 2006

Abstract
Flash photolytic studies have been made to elucidate the behavior of the intermediates and to obtain the rate constants of the elementary reactions, which are related to the reactions between acridine and acridan in benzene solutions. Two transient species, triplet and semireduced acridine, have been detected. The elementary reactions the rate constants of which have been measured are:
AT→A [1] k1=1–2×103sec−1
AT+AT→ [2] k2=6.0×109m−1sec−1
AT+O2→(A+O2*) [3] k3=6×109m−1sec−1
AT+AH2→2AH [4] k4=3×108m−1sec−1
2AH→(AH)2 [5] k5+k6=2–3×109m−1sec−1
→A+AH2 [6]
The quantity of AH produced in the presence of a small quantity of oxygen decreases with an increase in the oxygen concentration; if one assumes that Reaction [3] is mere deactivation, the decrease in acridine is too large to be expected from the values of k3 and k4. Hence, it has been inferred that O2* (or some other reactive intermediate) oxidizes AH2. The decrease in the yield of AH with the increase in the oxygen concentration has been attributed to the deactivation of O2* by a third substance. The other kinetic data have been found to be consistent with this scheme.
Silent Discharge Reactions in Aqueous Solutions. VI. Aqueous Solution of Chloralhydrate in Atmospheres of Helium and Argon
Authors: Yokohata Akira , Tsuda Satoru 
Published: July 2006

Abstract
Although most of the reaction systems hitherto treated are limited to acidic solutions in the series of this present research, this work has been extended to neutral solutions. Silent discharge leads to production of hydrochloric acid from neutral aqueous chloralhydrate. A linear correlation was observed between yield of hydrochloric acid and electric discharge current. This finding has been successfully interpreted in terms of absorbed dose, the value of which can be estimated at a given electric discharge current. Yields of hydrochloric acid were not significantly affected by chloralhydrate concentration between 1×10−2 m and 1×10−3 m. The experiments of the radical scavenging effect of cupric ion and bromide ion showed that KH+Cu2+⁄KH+CCl3CH(OH)2≈0.2 and KOH+Br−⁄KOH+CCl3CH(OH)2≈9, and also that the following formula holds approximately irrespective of kind of gas used in low solute concentration and dose rate used in this work: values of hydrogen atom G(HCl)\simeq3G(OH)+G(H). Moreover, these findings also suggested that the G values of and hydroxyl radical obtained in the acidic aqueous solution can be applied approximately to the neutral region. The relation of G(HCl) to solute concentration was qualitatively identical to gamma-ray irradiation, although they are different in detail because of the difference in value of LET and in the mechanism of radical formation.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. III. The Anion Radicals of Several Diesters of Biphenyl-o, o′- and p,p′-Dicarboxylic Acids
Authors: Hirayama Masatoshi 
Published: July 2006

Abstract
The ESR spectra of the anion radicals of dimethyl, diethyl, and diisopropyl esters of biphenyl-o, o′ and -p,p′-dicarboxylic acids, and of the di-t-butyl ester of the o, o′-derivative, have been studied. The anion radicals were prepared by electrolytic reduction in acetonitrile, and also by reduction with sodium and potassium metals in dimethoxyethane and tetrahydrofuran. The MO calculations of the spin densities were made by McLachlan’s method; all the splitting constants observed were assigned to the ring protons and the α-protons in the ester groups. A comparison of the experimental splittings with the calculated spin densities suggests that the anions ofp, p′-derivatives are in a planar conformation, while those of o,o′-derivatives have a twisted structure in which the twisting angle between the two rings was about 35–60°. A structural model was proposed for an ion complex formed between the anion of the o, o′-derivative and a sodium or a potassium cation.
ESR Study of Phenyl Nitric Oxide Radical
Authors: Kikuchi Osamu , Someno Kazuo 
Published: July 2006

Abstract
ESR spectra were obtained for phenyl nitric oxide radicals derived from phenyl hydroxylamines by oxidation with benzoyl peroxide, and the variation of hyperfine splitting constants with solvent was examined. Hyperfine splitting constants of nitrogen and NH proton varied with the polarity and hydrogen-bonding nature of solvent. This variation was explained by molecular orbital theory where the Coulomb integral of oxygen atom is assumed to vary with solvent. The sigma-pi parameters, QNH (in aH(NH)=ρNQNH), QN and Qo (in aN=ρNQN+ρOQO), were determined from experimental splitting constants of nitrogen and NH proton and the spin density calculated by McLachlan’s method. The values QNH=27.5, QN=30.5 QO=−13.6 were obtained and the latter two values could be used to calculate the nitrogen hyperfine splitting constant for diphenyl nitric oxide radical.
Spectrophotometric Studies of the Solution Equilibria and the Kinetics of the Substitution Reaction between Eriochrom Black T and Cobalt(II)-Ethylenediaminetetraacetate Chelate
Authors: Kodama Mutsuo 
Published: July 2006

Abstract
The solution equilibria and the kinetics of the substitution reaction between Eriochrom Elack T (BT) and cobalt(II)-EDTA chelate were studied spectrophotometrically. At the pH range from 8.50 to 9.50, BT was found to form only 1 to 1 normal chelate CoD with cobalt(II), the stability constant of which is 1020.0(μ=0.30). Kinetically, the substitution reaction was found to proceed through the following two simultaneous reaction paths,
i) HD2−+CoY2−\oversetk1+\ightleftharpoonsCoD−+HY3−
ii) HD2−\oversetrapid\ightleftharpoonsD3−+H+
D3−CoY2−−\oversetk2+\ightleftharpoonsCoD−+Y4−
and k1+ and k2+ were determined to be 0.23 l mol−1 sec−1 and 6.76×102 l mol−1 sec−1, respectively, at 20°C.
Altenin. IV. Compounds related to Altenin
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Mohri Ryotaro 
Published: July 2006

Abstract
Three compounds, ethyl 5-hydroxy-4, 6-dioxoheptanoate, ethyl 2-methyl-5-hydroxy-5-(1-hydroxyethyl)-4-oxotetrahydrofuroate and 5-phenyl-2-ethoxy-2-(1-hydroxyethyl)-3-oxotetrahy-drofuran, which have structures closely related to altenin, were synthesized from 3-acetoxy-2, 4-dioxopentane. These compounds produced the black spot disease in pears. As these compounds all possess the reductone grouping, it appears that this grouping is responsible for the phytopa-thogenic activity.
Studies of Heteroaromaticity. IV. The Thermal 1,3-Dipolar Cycloaddition of Fur- and 5-Nitro-2-furhydroxamoyl Chlorides with Olefinic and Acetylenic Compounds
Authors: Sasaki Tadashi , Yoshioka Toshiyuki 
Published: July 2006

Abstract
The corresponding isoxazolines and isoxazoles were prepared by 1, 3-dipolar cycloaddition with olefinic and acetylenic dipolarophiles by two methods, a) and b). Here, method a) means the routine method via nitrile oxide formation, while method b) means the new type of reaction named in the title. Method b) is concluded to be superior to method a) for the purpose of preparing isoxazoles and isoxazolines. The mechanism of the thermal 1, 3-dipolar cycloaddition is discussed.
Polymers Containing Disulfide Bonds. I. Derivatives of p-Benzene-bis(ω-S-alkylthiosulfate)
Authors: Murayama Ken , Kato Yasuo , Morimoto Saichi 
Published: July 2006

Abstract
Highly crystalline polymers were synthesized by the polymerization of p-benzene-bis(ω-S-alkylthiosulfate) (Remark: Graphics omitted.). Sodium sulfide was effective as a catalyst, but polymers obtained showed much more sulfur content than the theoretical value. The polymers (n≥2) possessed rubber-like characteristics.
Preparation and Properties of Organosilicon Surfactants
Authors: Meguro Kenjiro , Ochi Miyoko , Matsushita Noritaka 
Published: July 2006

Abstract
Surface-active polyethenoxy silicic esters were prepared by the reaction of tetraethyl silicate with various polyethenoxy higher alkyl ethers by the use of tetrabutyl titanate as a catalyst. Their properties as surfactant were compared with those of conventional nonionic surfactants. These compounds are soluble in many kinds of organic solvents, and have good dispersing power on such inorganic pigments as titanium oxide in organic media. The dispersing characteristics of these compounds in the inorganic pigments were tested in benzene, carbon tetrachloride, and monochlorobenzene by measuring the sedimentation volume. It was found that the compounds containing a chain of more than six ethenoxy groups were soluble in water. The surface tension of these water-soluble polyethenoxy silicic esters were determined in various concentration regions. In this paper, the preparation and properties of these compounds will be described.
Studies of Liquid-Liquid Partition Systems. V. The Formation of Mixed Dimers with Two Carboxylic Acids in Carbon Tetrachloride
Authors: Sekine Tatsuya , Isayama Muneo , Yamaguchi Sumiko , Moriya Hiromitu 
Published: July 2006

Abstract
The distribution of acetic, propionic and butyric acids, or of mixtures of two of these acids, between carbon tetrachloride and aqueous solutions has been studied at 25°C. The distribution data have been explained in terms of the partition of the acid monomer molecules and the dimerization of the monomer molecules in the organic phase. A salting-out effect has been observed upon additions of sodium perchlorate to the aqueous phase; this salting-out effect is larger in the order butyric&gt;propionic&gt;acetic acid. From the distribution data, the equilibrium constants for the distribution and the dimerization have been determined, and the formation constants for the mixed-dimer molecules have been compared with the statistical values. It has been concluded that the mixed-dimer molecules are equally stable or only a little less stable than had been statistically expected.
Dynamic Mechanical Behaviour of Organic Molecular Crystals. I
Authors: Danno Takaaki , Kajiwara Takashi , Inokuchi Hiroo 
Published: July 2006

Abstract
The forced resonance vibration method was applied to several needle-like organic crystals, triphenylene (I), 1,2,3,4-dibenzanthracene (II), coronene (III), anthracene-trinitrobenzene (TNB) complex (IV), perylene-TNB (V), coronene-TNB (VI), acridine-iode (VII), and acetyl-acetone-Gu (VIII), and their elastic constants were obtained. The observed Young’s moduli, E1 of these organic crystals were E1(I)=1.19×1010 dyn/cm2, E1(II)=2.81×1010, E1(III)=1.10×1010, E1(IV)=1.24×1011(V)=7.77×1010, E1(VI)=9.99×1010, E1(VII)=1.67×1011 and E1(VIII)=2.87×1010 dyn/cm2. These values are consistent with the E1-values of some aromatic hydrocarbons, as obtained from the acoustic velocity.
Reactions of Metal Chelates. I. The Reactions of Copper(II) Chelates of Some β-Diketones and Their Related Compounds with Glycine, Diglycine and Triglycine
Authors: Nakahara Akitsugu , Hamada Kazuko , Miyachi Isao , Sakurai Ken-ichi 
Published: July 2006

Abstract
The reactions of copper(II) chelates of β-diketones such as acetylacetone, benzoylacetone, dibenzoylmethane and benzoylacetaldehyde and of chelates of their related compounds such as salicylaldehyde and 2-hydroxyacetophenone with glycine or glycylglycine were investigated. Only bis(salicylaldehydato)copper(II) and bis(benzoylacetaldehydato)copper(II) reacted with glycine to form the respective glycinato-Schiff base complexes, whereas the other chelates did not react with glycine under the same condition. On the other hand, all the chelates except bis(dibenzoylmethanato)copper(II) reacted with glycylglycine to form the respective glycylglycinato-Schiff base complexes. The reaction at pH 4.5 between bis(salicylaldehydato)copper(II) and triglycine resulted in the hydrolytic cleavage of peptide bond, producing the salicylideneglycylglycinatocuprate(II) and free glycine. As the results of this investigation, five new copper(II) chelates were synthesized and characterized.
Spectrophotometric Studies on the Ion-pair Formation of Hexamminecobalt(III) and Tris(ethylenediamine)cobalt(III) Complexes with Halide and Sulfate Ions
Authors: Tanaka Nobuyuki , Kobayashi Yumiko , Kamada Minoru 
Published: July 2006

Abstract
The optical density of charge transfer spectra of some tervalent substitution-inert complex cations in an ultraviolet region increases by the addition of halide and sulfate ions. From the change in optical density the association constants were determined at ionic strength 0.07 (NaClO4) and 25°C. The values are 2.2±0.5 for Co(NH3)63+Cl−, 2.2±0.6 for Co(NH3)63+Br−, 0.71±0.5 for Co(NH3)63+ I−, 114±3 for Co(NH3)63+SO42−, 2.9±0.5 for Co(en)33+ Cl− and 102±8 for Co(en)33+SO42− respectively. The difference of these values from the reported values are related to the method for the measurements. Absorption maxima of the third absorption bands are obtained at 196 mμ for Co(NH3)63+ and at 210 mμ for Co(en)33+.
Electron Spin Resonance of Irradiated Single Crystals of Sodium and Potassium 1-Oximinopropionates
Authors: Hayashi Hisaharu , Itoh Koichi , Nagakura Saburo 
Published: July 2006

Abstract
ESR studies have been made with single crystals of sodium 1-oximinopropionate irradiated at −196°C and at room temperature. The principal values and axes of the g and hyperfine tensors of the trapped radicals have been determined. The analysis of the observed data has indicated that the σ-electron radicals CH3C(COO−)=NO are trapped at −196°C and at room temperature. It has been found that the electronic structures of the trapped radicals at these two temperatures are essentially the same, but that the environments of the radicals are very different from each other. After the crystal had been heated at 50°C for a week, the σ-electron radical vanished and the π-electron radicals, CH3C(OH)(COO−)NHO· and CH3CR’-(COO−)NRO·, appeared. The former may be formed in the solid state by adding a crystal water molecule to the unsaturated radical. The trapped radicals in irradiated single crystals of potassium 1-oximinopropionate were also studied at room temperature and after having been heated at 50°C. They are the σ-electron radical and the π-electron radical respectively, with structures similar to those of the sodium salt. The radical pairs have been observed in irradiated single crystals of the sodium salt at −196°C.
Convenient Syntheses of 1,2-Ureylenecyclopentane Derivatives
Authors: Takaya Takao , Yoshimoto Hataaki , Imoto Eiji 
Published: July 2006

Abstract
Three Convenient syntheses of cis-1, 2-ureylenecyclopentane (VI) and cis-cis-3-methyl- 1, 2-ureylenecyclopentane (VIa), from 2-carbethoxycyclopentanone (I) and 5-methyl-2-carbethoxycyclopentanone (Ia) respectively, are described. The Curtius degradation of cis-2-aminocyclopentanecarboxylic acid derivatives took place without cis-trans isomerization. The hydrogenation of ethyl 3-methyl-2-ureidocyclopent-1-ene-1-carboxylate at 70°C gave two isomeric products, the major (IIIa), cis-cis-, and the minor (IIIb), cis-trans-3-methyl-2-ureido-1-carbethoxycyclopentane.
The Alkaline Sulfide Reduction of Aromatic Nitro Compounds. XII. ESR Studies of the Alkaline Sulfide Reduction of the Aromatic Nitro Compound
Authors: Hashimoto Shizunobu , Sunamoto Junzo , Aoki Akira 
Published: July 2006

Abstract
The ESR techniques were used in order to examine the presence of the radical species in the alkaline sulfide reduction of aromatic nitro compounds and in the photooxidation of an aqueous monosulfide solution. The ESR spectra were clear when observed by ultraviolet-light irradiation on an aqueous monosulfide solution: they were the signals of a singlet, with a g-value of 2.002±0.001 and a maximum slope width of 3.1 gauss, and a doublet, with a g-value of 2.00±0.001 and a coupling constant of 114 gauss. The singlet was identified as the signal of the sulfide ion radical, S·−, while it was most reasonable to assume the doublet to be signals due to the interaction of the sulfide ion radical with the hydrosulfide or the hydroxide in the solution. On the other hand, ESR spectra were also observed in the reaction of sodium m-nitrobenzene sulfonate with an aqueous monosulfide solution; these spectra were identical with the sulfide ion radical and the radical-anion of the nitro compound. On the basis of the results obtained, we have discussed the mechanisms of the alkaline sulfide reduction of aromatic nitro compounds and these reduction intermediates.
Syntheses of Reductones. A New Method of Synthesizing 2-Acetoxy-1, 3-dicarbonyl Compounds
Authors: Sugiyama Noboru , Yamamoto Makoto , Takano Tadao , Kashima Choji 
Published: July 2006

Abstract
2-Acetoxy-l, 3-dicarbonyl compounds were synthesized by two methods, one consisting of the condensation of 1, 3-dicarbonyl compounds with an electrophilic reagent, followed by acetoxylation. By this method three new compounds, ethyl 5-phenyl-2-acetoxy-3-oxopentanoate (XVII), ethyl 5, 5-diphenyl-5-hydroxy-2-acetoxy-3-oxopentanoate (XVIII), and ethyl 2-acetoxy-3-oxoheptanoate (XIX), were obtained. The other method consisted of the acetoxylation of 1, 3-dicarbonyl compounds, followed by condensation. By this method three other new compounds, 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxohexane (IV), 6-phenyl-6-hydroxy-3-acetoxy-2,4-dioxo-hexane (VIII), and 6-phenyl-3-acetoxy-2, 4, 6-trioxohexane (X), were obtained.