bluuebunny/crossref_metadata_2025 huggingface dataset:
An MO-Theoretical Illumination for the Principle of Stereoselection
Authors: Fukui Kenichi
Published: July 2006

The principle of the stereoselection in organic chemistry has been discussed from the point of view of the molecular orbital theory. The stereoselectivity in the stereospecific ring-closure of conjugated polyenes and the stereospecific ring-cleavage of unsaturated carbon cycles, trans-1,2-noncycloadditions, cis-1,2-additions and cis-1,3-dipolar additions have been accounted for with a qualitative generalization. In many cases the symmetry relationship of certain particular molecular orbitals (“frontier orbitals”) plays a conspicuously significant role in the steric control of stereochemical processes. This may be put in contrast with the role of the frontier electron density in the orientation process in organic reactions.
Syntheses of dl-Tetrahydroanhydrodesoxyaucubigenin and Related Compounds
Authors: Kurosawa Kazu , Obara Heitaro , Uda Hisashi
Published: July 2006

The racemic tetrahydroanhydrodesoxyaucubigenin, one of the derivatives from a glycoside, aucubin, has been synthesized using cis-cis-2-(2′-hydroxyethyl)-5-methoxycarbonylcyclopentane-carboxylic acid δ-lactone as an intermediate. 6,7-Dimethoxycarbonyl-2-oxa-bicyclo[3.3.0]-octane has also been synthesized, and the mechanism of the base-catalyzed rearrangement of the naturally-derived tetrahydroanhydroaucubigenin p-toluenesulfonate has been elucidated.
Vinylpolymerisation. CXXIX. Pfropfung von Methylmethacrylat auf Naturkautschuk in Abwesenheit von Initiatoren
Authors: Kondo Mitsuru , Yamada Kuniyoshi , Takemoto Kiichi , Imoto Minoru
Published: July 2006

The graft polymerization of methyl methacrylate on natural rubber was studied in an aqueous suspension at 90°C, in the absence of initiators. It was found that methyl methacrylate could be grafted fairly smoothly on uncured natural rubber crepe and latex, both of which had previously been extracted with acetone.
The Ring-opening Polymerization of Ethylene-methylphosphite
Authors: Shimidzu Takeo , Hakozaki Tomio , Kagiya Tsutomu , Fukui Kenichi
Published: July 2006

Several Lewis acids have been found to be effective catalysts for the polymerization of ethylene-methylphosphite, giving a solid polymer with a poly(ethylene-methylphosphonate) structure. The use of Al(C2H5)3 gave a wax-like polymer with the structure of poly(ethylene-methoxy-phosphinate), while Na and Li in liquid NH3 at −78°C produced a jelly-like polymer partly composed of poly(ethylene-methylphosphite).
Phosphorylation via the Oxidation of Phosphite. II. The Preparation of the Diesters of Phosphorous Acid by the Reaction of Alcohols with Ethyl N-Phenylimino Phosphite and Acids
Authors: Mukaiyama Teruaki , Osaka Kazutoshi
Published: July 2006

The diesters of phosphorous acid were prepared in good yields by the reaction of primary or secondary alcohols, such as methanol, ethanol, and s-butanol, or of phenols, such as phenol, p-chlo-rophenol and p-cresol, with ethyl N-phenylimino phosphite and p-toluenesulfonic acid monohy-drate. Similarly, when carboxylic acids, such as acetic acid, benzoic acid, p-chlorobenzoic acid and trichloroacetic acid, were used in place of the acid monohydrate in the above experiment, the diesters of phosphorous acid were also obtained. Ethyl N-n-propylimino or ethyl N-isopropylimino phosphite could be successfully used in place of ethyl N-phenylimino phosphite in the above experiments. Further, various derivatives of methylphosphinic acid, such as ethyl dicyanomethyl-, ethyl cyanocarboethoxymethyl- and ethyl dicarboethoxymethylphosphinate, were obtained by the reaction of ethyl N-phenylimino phosphite, p-toluenesulfonic acid monohydrate and active methylene compounds, such as malononitrile, ethyl cyanoacetate and diethyl malonate.
The Determination of Micro Amounts of Polythionates. IV. A Photometric Method for the Determination of Tetrathionate by Decomposition with Sodium Sulfite
Authors: Iwasaki Iwaji , Suzuki Shigeru
Published: July 2006

A new photometric method for the determination of tetrathionate by means of its decomposition with sulfite has been developed. It is based on the formation of thiosulfate equivalent to the tetrathionate, and on the photometric determination of thiosulfate by measuring its decoloration of an iodine solution. 5×10−6–1×10−3  m (1 mg./l.–0.2 g./l.) of tetrathionate can be determined easily and rapidly within a range of error of ±2×10−6–2×10−5  m (0.4 mg./l.–4 mg./l.) by using 20 ml. of a sample. The tetrathionate solution is decomposed with sodium sulfite in a slightly alkaline medium. After the completion of the decomposition reaction, a formaldehyde solution is added to mask the interference of the excess sulfite remaining and this solution is acidified with acetic acid. Then the standard iodine solution is added. The absorbancy of the solution is measured at the wavelength of 372 or 440 mμ 20 min. after the addition of an iodine solution. By this method tetrathionate can be determined, even when it is coexistent with thiosulfate and sulfite in up to similar amounts. Many substances, such as aluminum, calcium, cadmium, magnesium, zinc, silicate, nitrate, sulfate, phosphate, chloride and fluoride, do not interfere, but iron(II, III), manganese(II), copper(II) and sulfide do interfere.
Copper(II) Halide Complexes with Substituted Pyridine N-Oxides
Authors: Muto Yoneichiro , Jonassen Hans B
Published: July 2006

Pyridine N-oxide copper(II) chloride, the structure of which has recently been elucidated by X-ray analysis [J. C. Morrow and H. L. Schäfer, private communication], has a subnormal magnetic moment (0.85 b.m. [J. V.Quagliano, J. Fujita, G. Franz, D. J. Phillips, J. A. Walmsley and S. Y. Tyree (J. Am. Chem. Soc., 83, 3770 (1961)]). It consists of a binuclear molecule [Cu(C5H5NO)Cl2]2 in which copper atoms are bridged in pairs by two oxygen atoms. In this work, copper(II) complexes with the empirical formulae of CuX2L, CuX2L2 and CuX2LY (X=Cl, Br;L=pyridine N-oxide, 3-picoline N-oxide, 4-picoline N-oxide, 4-chloropyridine N-oxide, 2,4-lutidine N-oxide, 2,4,6-collidine N-oxide, 4-nitroquinoline N-oxide; Y=N,N′-dimethylformamide, dimethylsulfoxide) have been prepared, and magnetic and spectral studies of these complexes have been made. The room-temperature magnetic susceptibilities of CuX2L complexes have been found to be correlated with the pKa (acid-dissociation constant) values of the attached N-oxides. The absorption band in the 735–900 mμ region (the so-called copper band) in the solid-state reflectance spectra of CuX2L complexes has been found to shift towards a lower frequency as the ligand field strength decreases, and a good parallelism between the frequencies and the magnetic moments has been observed. The effect of the attached ligand on the magnetic interaction has been discussed in terms of the electronic effect of the substituent on the pyridine ring. The infrared spectral data on the N–O stretching frequency indicate the absence of Cu–O–Cu linkage in the CuX2L2 complexes with normal magnetic moments.
Calculation of the Three π–π* Absorptions of Conjugated Systems by Hückel MO Method
Authors: Nishimoto Kichisuke
Published: July 2006

Correlation relations between the Hückel molecular orbital energies and the absorption wavelengths of the 1La, 1Lb, and 1Bb species of an alternant hydrocarbon are presented. After a small modification, the present relations are applied fairly well to the calculations of the electronic spectra of α-substituted hydrocarbon and N-heterobenzenes. This shows us that the nature of the electronic spectra of these compounds are very similar with those of parent hydrocarbon. On the other band, the calculation for β-substituted derivatives does not give good results, although the agreement between the calculated and observed values is semi-quantitatively satisfactory. This should be attributed to the complicated configuration interaction scheme between the lower excited configurations of the molecule.
The Oxidation of Acetylacetone in the Presence of Cobaltous Ions
Authors: Koga Tadashi , Hara Tadashi
Published: July 2006

Concerning the oxidation of toluene and p-xylene with atmospheric oxygen at 90°C in glacial acetic acid in the presence of cobaltous acetate and acetylacetone (HAAH), it was found that the reaction proceeds smoothly only at the mole ratio of [HAAH]/[Co2+]=2. When the absorption rate of oxygen was then measured for acetic acid solutions containing cobaltous ions and HAAH, the following results were obtained:

at [HAAH]⁄[Co2+]≤3, −d[O2]⁄dt=Ka[HAAH]1⁄2[Co2+]−1⁄3

at [HAAH]⁄[Co2+]≥4, −d[O2]⁄dt=Kb[HAAH][Co2+]1⁄4

These rates agree well with those derived by means of elementary equations in the radical chain reactions. It was further supposed, on the basis of the elementary equations, that active intermediates, such as Co3+, [Co3+(AAH−)2]+, and some radicals, were produced smoothly at the mole ratio of [HAAH]/[Co2+]=2. However, ketones, such as acetonylacetone and ethyl acetoacetate, were still active even at the mole ratio of [ketone]/[Co2+]=3. This seems to stem from the differences in complex stabilities between cobalt and HAAH or other ketones.
The NMR Analysis of the Water of Crystallization in Beryl
Authors: Sugitani Yoshinori , Nagashima Kozo , Fujiwara Shizuo
Published: July 2006

The existence of two types of protons in beryl was proved by the proton magnetic resonance technique; one is as a molecular form of water in the channel of the crystal, while the other is as a hydroxyl-ion replacing O2− ion of the crystal lattice. The proton-proton line of the water was found to be parallel to the c-axis of the crystal.
Colloid Chemical Studies of Phase Diagrams of Binary Polyoxyethylene Nonylphenyl Ether - Water Systems
Authors: Kenjo Kazutoshi
Published: July 2006

Colloid chemical studies of the phase diagrams of binary systems of aqueous polyoxyethylene nonylphenyl ethers with different degrees of the polymerization of ethylene oxide, n, have been undertaken. The phase diagrams obtained have been divided into the heterogeneous region 1, existing in the range of temperature higher than cloud points; the homogeneous phase region II; the heterogeneous region III, existing below the II region; and the solid phase region IV. The II region contains a gel-like hardening region. The III region has been further divided into two sub-regions, on the higher and lower concentration sides; these subregions contain one hardening region each. The molecular and micellar structure models of these hardening regions have been presented. An unusual zone has been found in the phase diagram of the system for n=7.5 its state has also been discussed. Further, the mechanisms of the phase separation and phase inversion have been proposed, and three different types distinguished for the phase separation at the cloud point. A functional relationship has been found between the cloud point, the water content of an aqueous solution at the cloud point (the water affinity), and the n value. A linear relation has also been found between the solidification points of 100% surfactants and the ethylene oxide contents of the surfactants.
Catalytic Asymmetric Benzaldehyde Cyanohydrin Synthesis with Synthetic Optically Active Polymer. III. N-Substituted Poly-(s)-isobutylethylenimine
Authors: Tsuboyama Sei
Published: July 2006

Asymmetric syntheses of benzaldehyde cyanohydrin in the presence of polymers of N-methyl-,N-ethyl- and N-benzyl-(s)-2-isobutylethylenimine as catalysts have been studied. The selectivity of these polymers was poor (optical yield of (−)-isomer obtained; 0–1%) compared with that of a non-N-substituted polymer (20%). It seems that the large difference in the optical yield can be ascribed to their conformation. As to the polymer being capable of promoting the reaction asymmetrically, it is assumed that the isobutyl group and a helical form are the responsible factors. On the basis of these findings, a model for the addition step has been suggested in order to explain the observed result.
Studies of the Solution Properties of Co-polymer. I. Styrenepolysulfone
Authors: End\={o} Ry\={u}ichi , Manag\={o} Tomoyuki , Takeda Masatami
Published: July 2006

Styrenepolysulfone was polymerized and then, for its fractionation, tetrahydrofuran and methanol were used as solvent and precipitant respectively. The viscosities and osmotic pressures of fractions of this co-polymer were examined in tetrahydrofuran. The relation between the intrinsic viscosity and the molecular weight, [η]=0.389×10−4\barMn0.78, was thus obtained. The unperturbed molecular dimension was calculated by the Fixman-Stockmayer method. The results were then compared with the calculated end-to-end distance of the hypothetical freely-rotating chain. The steric parameter, σ=1.53, was also obtained and compared with that of polystyrene.
Dipole Moment and Molecular Structure of Copolymers. III. Dipole Moment of p-Methoxystyrene-Styrene Copolymers and p-Chlorostyrene-Styrene Copolymers
Authors: Kotera Akira , Suzuki Keizo , Matsumura Kimiyoshi , Shima Mikiko , Joko Etsuro
Published: July 2006

The p-methoxystyrene monomer has been synthesized from anisole through p-methoxyacetophenone and p-methoxyphenyl methyl carbinol. Then copolymers of p-methoxystyrene and styrene have been prepared. The dielectric properties of the copolymers in a benzene solution have been measured, and it has been found that the value of the dipole moment, μ, of the p-methoxystyrene monomer unit in the copolymers increases with an increase in the styrene content, e. g., from 1.21 D (for poly-p-methoxystyrene) to 1.32 D (for the copolymer in which the mole fraction of p-methoxystyrene is 0.175) at 20°C. The variation in the value of μ has been discussed in view of the detailed arrangement of polar monomer units. The theory concenring the relation between the dielectric polarization and the detailed structure of the copolymer molecule developed in the preceding paper, Part I, has been applied to the experimental results. In addition, a similar analysis has been made for the dielectric polarizations of the p-chlorostyrene-styrene copolymers which had been measured previously by one of the authors.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. IX. The Nitrates of Glucose
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko
Published: July 2006

We have measured the rotatory dispersion (RD) and the ultraviolet absorption of twelve nitrates of glucopyranosides carrying a nitrate chromophore, –O–NO2, in the position of the carbon atoms 1, 2, 3, 4, and 6. On the basis of the experimental results and of those results already reported concerning four nitrates, studies have been made as to the correlation between the configuration and the Cotton effect. The sign of the Cotton effect has been determined by the RD curve as well as by the dispersion constant as computed from the dispersion data. A regular relation has been found, namely, irrespective of the position of the nitrate group on the carbon atom, α-glucosides with α nitrate chromophore in the α- or (d)-configuration show negative Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is positive. On the contrary, α-glucosides with a nitrate chromophore in the β- or (l)-configuration show positive Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is negative.
The Cation Effect on the Polarographic Reduction of cis-Dioxalatodiaquochromate(III) and Trioxalatochromate(III) Ions
Authors: Tanaka Nobuyuki , Itabashi Eiki , Tamamushi Reita
Published: July 2006

The cation effect on the polarographic reduction of cis-dioxalatodiaquochrormate(III) and trioxalatochromate(III) ions has been reported. cis-Dioxalatodiaquochromate(III) ions give an irreversible wave corresponding to a three-electron reduction in the solutions of univalent electrolytes, while they give a double wave in the solutions of bivalent electrolytes, the first wave being of a one-electron reduction and the second wave, of a two-electron reduction. Trioxalatochromate(III) ions are reduced to chromium(0) in the univalent and the bivalent electrolyte solutions at more negative potentials than cis-dioxalatodiaquochromate(III) ions. The reduction potentials of these complex anions depend on the nature and the concentration of cations of electrolytes present in the solution, and shift to less negative potentials with increasing ionic charges of the cation and, at the constant ionic charge, with decreasing radii of the hydrated ion and increasing concentrations of the cation present. The cation effect was explained by taking into consideration of both the structure of the electrical double layer and the formation of ion-pairs.
The Automatic Measurement of the Ohmic and Capacitive Components of the Impedance on a Platinum Electrode in Transient States
Authors: Shibata Shigeo
Published: July 2006

A new technique with an electronic circuit is described in which the ohmic and the capacitive components of the impedance of the electrode-solution interface may be registered simultaneously and continuously as a function of the time at a given frequency during polarization with a constant anodic or cathodic current. Impedance measurements were made on a smooth platinum in 2 n perchloric acid, 2 n sodium perchlorate and 2 n sodium hydroxide solutions in the region of oxygen deposition. According to the observed behavior of the impedance of the electrode, the oxide film on the electrode surface may be completed anodically through three stages; first, the adsorption of the hydroxyl radical; second, the formation of oxide (II), and finally, the conversion of this oxide to one of a higher grade. The dependence of the value of the electrode capacity at the first stage on the pH of the solution is discussed on the basis of the ion-exchange adsorption of cations and anions on the electrode surface covered by the hydroxyl radicals.
The Synthesis of Glycidylferrocenes and Related Compounds
Authors: Watanabe Hamao , Motoyama Izumi , Hata Kazuo
Published: July 2006

Ferrocene derivatives with one or two glycidyl substituents, desired for the formation of polymeric ferrocene compounds, were synthesized by the epoxidation of chlorohydrin compounds obtained from the products of the addition of ferrocenyllithium to epichlorohydrin at −40–−78°C. In the course of this synthesis, mono- and di-chlorohydrin compound and a disubstituted ferrocene with a 3-chloro-2-hydroxypropyl and a glycidyl substituent were isolated. All of them are stable liquid compounds. The investigation of the relationship between the reaction conditions and the yield of glycidylferrocenes revealed that the larger molar ratio of each reactant to ferrocene at each reaction step causes a higher conversion into glycidylferrocenes. In the epoxidation reaction of chlorohydrins with caustic alkali, a small amount of ethers, formed by the reaction of epoxides and the solvent ethanol, was obtained under some reaction conditions. In all cases, a small amount of biferrocenyl was isolated; the formation of this compound was considered to be attributable to the Wurtz-type coupling reaction of ferrocenyl radicals. The structures of all these products were confirmed by their infrared absorption spectra and, in part, by the NMR spectra.
The Direct Formation of Biferrocenyl and Polyferrocenyls from Ferrocenyllithium
Authors: Watanabe Hamao , Motoyama Izumi , Hata Kazuo
Published: July 2006

In the presence or absence of n-butyl bromide, ferrocenyllithium and cobaltous chloride reacted to give various polyferrocenyls and butylated polyferrocenyls. They were isolated, mainly by alumina chromatography, and their structures were established, principally from the NMR spectra, to be heteroannularly-bonded ones. The formation of these compounds is considered to be due to the coupling reactions of the ferrocenyl radical, the ferrocenylene biradical and the butyl radical, which were formed by homolytic fissions of some reactive intermediate and butyl halide. The presence of the alkyl halide greatly affected the sorts and yields of the products. No cyclic polyferrocenylene was obtained. The “9—10 rule” concerning the infrared spectra of ferrocene derivatives was found not to apply to di-substituted biferrocenyls. It was found, by a study of the X-ray diffraction patterns and the infrared spectra, that terferrocenyl crystallizes in polymorphic forms according to the method and the solvent of crystallization. The polymorphism may be attributable to the rotational isomerism around the central ferrocene nucleus.
Studies of Organic Catalytic Reactions. III. The Hydration Mechanism of Nitriles to Amides with Nickel Catalysts
Authors: Watanabe Ken-ichi , Sakai Koji
Published: July 2006

Benzonitrile, benzyl cyanide, acetonitrile and 2-cyanopyridine give the corresponding amides by the hydration with nickel catalysts and water. The effect of pyridine and thiophene on the hydration has been investigated. In general, the yield of amides increases upon the addition of a suitable amount of pyridine. On the contrary, the reaction is distinctly suppressed by the addition of thiophene. This fact is in striking contrast to the effect on the hydrogenation of nitriles. The correlation of the catalytic functions in hydration and the hydrogenation of nitriles has been studied, and the hydration mechanism with nickel catalysts has been discussed.
The Crystal Structure of 1,2,3,4-Tetrachlorobenzo[g]sesquifulvalene
Authors: Nishi Yoriko , Sasada Yoshio , Ashida Tamaichi , Kakudo Masao
Published: July 2006

The molecular structure of 1,2,3,4-tetrachlorobenzo[g]sesquifulvalene has been ascertained by X-ray crystal analysis. The crystal of this substance is monoclinic, with four molecules in a unit cell of dimensions: a=21.31, b=16.88, c=3.83 Å, and β=93.3°, the space group being P21/a. The crystal structure was determined by the Harker-Kasper inequality and the Sayer’s method. The atomic coordinates and the anisotropic temperature factors of each atom were refined by the block-diagonal-matrix least-squares method. The average length of the C–Cl bonds is 1.705 Å, a value which is in good agreement with those of several chlorobenzenes. In the sesquifulvalene skeleton, longer and shorter bonds are disposed as may be expected from the conventional chemical formula. The average length of the longer bonds is 1.461 Å, while that of the shorter ones is 1.354 Å. The mean C–C bond length in the benzene ring is 1.413 Å. The whole molecule is not on a plane, although the component ring systems are nearly planar. The five-membered ring and the seven-membered ring twist to each other by an angle of about 31° around the bond connecting these two rings. This might be due to the repulsion forces between chlorine and hydrogen atoms which approach each other closely. The plane of the seven-membered ring makes an angle of about 5° with that of the six-membered ring.
The Oxidation of Chloromethyl Compounds with Lead Tetraacetate
Authors: Yukawa Yasuhide , Sakai Mitsuru
Published: July 2006

In studying the reaction of styrene, olefins, vinyl ethers and vicinally-substituted compounds with lead tetraacetate, it was shown that the methyl group of 9-chloro-9-methylfluorene was easily acetoxylated with lead tetraacetate. This novel reaction was then applied to 1, 1-diphenylethyl chloride, 1-phenylethyl chloride and t-butyl chloride. In every case the methyl group of chlorides with an α-methyl group was acetoxylated preferentially.
The Solvent Effect on the Equilibrium of a Chemical Reaction in a Non-electrolyte Solution: Application to the Keto-enol Tautomerism and Dimerization of Nitrogen Dioxide
Authors: Tanaka Satohiro
Published: July 2006

A simple lattice theory of a non-electrolyte solution in which the equilibrium of chemical reaction is reached has been presented and compared with the data of the enolization of ethyl acetoacetate in various solvents and with those of the dimerization of nitrogen dioxide in chloroform. Predicted linear relationships has been obtained for the data of the enolization in non-polar solvents, but they could not be obtained for the reaction in ethyl alcohol or for the dimerization of nitrogen oxide in chloroform. The van’t Hoff-Dimroth relation has been derived by the present theory.
The Charge-transfer Complex and the Photochemical Reactions of Anthracene with Sulfur Dioxide in Various Solvents
Authors: Nagai Toshikazu , Terauchi Kenichi , Tokura Niichiro
Published: July 2006

The equilibrium constant, K, of the 1:1 charge-transfer complex formation of anthracene with sulfur dioxide has been estimated by spectrophotometric measurements to be 0.33 in carbon tetrachloride at 15°C. The values of ΔH (−4.8 kcal.mol−1) and ΔS° (−19 cal.deg−1mol−1) have been derived. The K value is nearly zero when estimated in the longer wavelength region, indicating that a contact charge-transfer complex is involved. A sort of contact charge-transfer complex of anthracene-SO2 is also observed in benzene. Irradiations by a high-pressure mercury lamp of anthracene with sulfur dioxide in various solvents have been carried out. In solvents such as n-hexane and carbon tetrachloride, which have no interaction with sulfur dioxide, anthracene gives sulfur-containing substances, such as anthracene-9-sulfonic acid (I) and dianthranyl-(9.9′)-sulfonic acid-(10) (II). On the contrary, in benzene or in carbon disulflde, no product such as the sulfonic acid, the dimer or the endoperoxide of anthracene is produced, indicating that the interaction of anthracene with sulfur dioxide is diminished by the solvent - sulfur dioxide interaction. A suggestion was made that the activated intermediate which induced the formation of I and II was of a singlet character.
Reactions of the Benzil-Triethyl Phosphite Adduct
Authors: Mukaiyama Teruaki , Kumamoto Takanobu
Published: July 2006

The decomposition of benzil-triethyl phosphite adduct in the presence of copper powder or cupric sulfate has been studied. When benzil, triethyl phosphite and cupric sulfate were treated in boiling toluene. cis-dibenzoylstilbene and triethyl phosphate were obtained. When the reaction was carried out in the presence of active hydrogen compounds, such as alcohol, carboxylic acid and amine, the corresponding benzoin derivatives were obtained. Further, when the adduct was decomposed in the presence of phenyl isocyanate or dicyclohexylcarbodiimide, 3, 4, 5-triphenyl-4-oxazoline-2-one or 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline was obtained, along with triethyl phosphate.
The Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. VII. The Synthesis of Peptide Derivatives Corresponding to Positions 11 to 18 in the Corticotropin Molecule
Authors: Otsuka Hideo , Inouye Ken , Kanayama Makoto , Shinozaki Fusako
Published: July 2006

The derivatives of lysyl-prolyl-valyl-glycyl-arginyl-arginine, lysyl-prolyl-valyl-glycyl-lysyl-arginyl-arginine and lysyl-prolyl-valyl-glycyl-lysyl-lysyl-arginyl-arginine, which correspond to the amino acid sequences in positions 11—14 plus 17—18, 11—14 plus 16—18, and 11—14 plus 11—18 of the corticotropin molecule respectively, have been obtained as intermediates for the synthesis of adrenocorticotropically active peptides.
The Radiation-Induced Addition of Hydrogen Chloride to Ethylene
Authors: Terakawa Akira , Nakanishi Jun , Hirayama Toru
Published: July 2006

In a stainless steel autoclave, ethylene and hydrochloric acid or dried hydrogen chloride were irradiated with cobalt-60 gamma-rays. n-Butyl chloride and ethyl chloride were thus produced efficiently, unlike as when an ultraviolet light or catalyst was used. The products were quantitatively analyzed by gas chromatography. This reaction was supposed to be a vapor-phase radical chain reaction; the proposed reaction mechanism agreed well with our results. The selectivity of ethylene to the products was considered to be practically 100%. The G values of ethyl chloride, n-butyl chloride and the ethylene consumed, using the ratio of the total absorbed dose to ethylene, were calculated to be 16000, 10000 and 35000 respectively at 50°C and at a dose rate of 1.10×104r./hr. The ratios of the rate constants for ethyl chloride and n-butyl chloride were 366, 499 and 580 at 50, 40 and 15°C respectively, and the apparent activation energies for ethyl chloride and n-butyl chloride were calculated from the reaction rates to be 6.94 and 8.95 kcal./mol. respectively.
The Barium Content of Barite-forming Hydrothermal Waters as Exemplified by Tamagawa Hot Spring Waters
Authors: Ichikuni Masami
Published: July 2006

An estimation of the barium concentration in Tamagawa Hot Spring water was made on the basis of the partition of lead between spring waters and barite deposits precipitated from the waters. As the lead content of the waters and the chemical composition of the deposits are already known, the barium concentration can be computed by the use of the following relation:

D=(\fracPbBa)S⁄(\fracPbBa)L

where D is the partition coefficient of lead, and where S and L denote the solid and liquid phases respectively. A value of 2±1 mg./1. was obtained for the barium concentration in the water issuing from the vents. It was pointed out that the water is supersaturated with barium sulfate. This supersaturation may be due to the addition of a considerable amount of sulfates, probably formed by supergene processes, to the original thermal water. The genesis of hydrothermal barite deposits was also discussed.
Asymmetric Synthesis with Sugar Derivatives. I. The Conjugate Additions of Grignard Reagents to α, β-Unsaturated Esters of Sugar Derivatives
Authors: Kawana Masajiro , Emoto Sakae
Published: July 2006

Partial asymmetric syntheses were carried out in the reaction of Grignard reagents with crotonic and cinnamic esters of 1,2:5,6-di-O-cyclohexylidene-d-glucose, 1,2:5,6-di-O-isopropylidene-d-glucose, 1,2-O-isopropylidene-5-deoxy-d-xylose and (−)-menthol. The reaction of 3-O-crotonyl-1,2:5,6-di-O-cyclohexylidene-d-glucose (Ic) with phenylmagnesium bromide, followed by the hydrolysis of the resulting ester, gave (−)-3-phenylbutyric acid (III) in 33% optical and 12% synthetic yields, while in the presence of cuprous chloride as a catalyst, III was obtained in 74% and 58% yields respectively. The reaction of 3-O-crotonyl-1,2-O-isopropylidene-5-deoxy-d-xylose (Ie) with phenylmagnesium bromide gave (+)-acid (III) without cuprous chloride in 16% optical and 32% synthetic yields and (−)-acid (III) with cuprous chloride, in 58% and 61% yields respectively. The reaction of 3-O-cinnamoyl-1,2:5,6-di-O-cyclohexylidene-d-glucose (IVc) with benzylmagnesium chloride, followed by the saponification of the resulting ester, gave (−)-3,4-diphenylbutyric acid (VI) in 18% optical and 62% synthetic yields without cuprous chloride, and in 17% and 58% yields with cuprous chloride. In the formation of acid (VI), cuprous chloride seemed to have no effect on optical and synthetic yields nor on the change in the sign of optical rotation. The steric courses of these reaction are discussed.
A Preliminary Study of the Carboxylation and Decarboxylation of Some Sulfides
Authors: Tagaki Waichiro , Ueyama Kenji , Minamida Isao , Kim Yong He , Ikeda Yoshinori , Oae Shigeru
Published: July 2006

Some sulfides with benzylic hydrogen have been carboxylated by carbonating the respective carbanions generated with dimsylsodium in dimethyl sulfoxide. The resulting mercaptocarboxylic acids have then been found to have considerably-enhanced rates of decarboxylation reaction.
The Crystal Structure of Tris(l-propylenediamine)cobalt(III) Bromide and the Absolute Configuration of the Complex Ion, [Co l-pn3]3+
Authors: Iwasaki Hitoshi , Saito Yoshihiko
Published: July 2006

Crystals of L-[Co l-pn3]Br3 (pn: propylenediamine) were prepared and their crystal structure was completely determined by means of X-rays. They are hexagonal, with the space group P63; a=11.08±0.03,c=8.59±0.02Å and Z=2. The structure is essentially ionic, consisting of complex ions and bromide anions. A complex ion has a three-fold axis of symmetry through the central cobalt atom. Five-membered Co-pn rings are puckered, and the C–C bonds in these rings are nearly parallel to the threefold axis. The methyl carbon bonds are equatorial with respect to the plane of the ring. The absolute configuration of the complex ion has been determined by using the absorption-edge technique. The Llll-type complex ion has been found to be laevorotatory with respect to the NaD lines. By the introduction of an asymmetric carbon atom into the ligands, the absolute configuration of a series of tris(bidentate)-complexes could be successfully correlated to the configurational series in organic compounds.
Chronopotentiometry of Tris(ethylenediamine)chromium(III) Ions in Various Supporting Electrolyte Solutions
Authors: Tanaka Nobuyuki , Yamada Akifumi
Published: July 2006

The reduction of tris(ethylenediamine)chromium(III) ions at the dropping mercury electrode has been studied chronopotentiometrically in various supporting electrolyte solutions. The electrolysis at constant cathodic current in an acid solution gives a well-defined chronopotentiogram which corresponds to the one-electron reduction of chromium(III) to chromium (II). The anodic chronopotentiogram which is obtained by the current-reversal techniques is clearly separated from the cathodic one. Two cathodic steps are obtained in alkaline ethylenediamine solutions, and two anodic steps, at the current reversed. No chemical reaction involving hydrogen ions or ethylenediamine takes place prior to the electron transfer. The presence of very small amount of surface-active substances was found to improve the shape of chronopotentiograms. In the presence of EDTA, the one-electron cathodic chronopotentiogram splits into two steps.
Chemical Studies of Minerals Containing Rarer Elements from the Far East District. LX. Thalenite from Suishoyama, Kawamata-machi, Fukushima Prefecture, Japan
Authors: Nagashima Kozo , Kato Akira
Published: July 2006

Chemical studies of thanlenite from Suishoyama pegmatite, Fukushima Prefecture, showed its composition to be very close to the ideal formula, Y2Si2O7, and to a selective distribution pattern of rare earths belonging to the thortveitite-type as defined by Goldschmidt and Thomassen. The X-ray powder studies disclosed a metamict state hitherto unknown in this species, and the original state could be recovered by thermal treatment. Optical and other properties: color, colorless to light gray; luster, resinous; optical properties, α=1.709±0.002, β=1.716±0.002, γ=1.723±0.002, (−)2V∼70°, ρ<v; specific gravity, 4.16, hardness; 6\frac12. Chemical analysis: SiO2, 30.68%; Al2O3, 0.10%; Fe2O3, 0.17%; ΣY2O3, 64.89%; UO2, 1.12%; ThO2, 0.20%; CaO,0.35%; MnO, 0.38%; MgO, 0.33%; Na2O, 0.02%; H2O(+), 1.56%; H2O(−), 0.11%; total, 99.91%.
The Dipole Moment and Polarizability in the n–π* Excited State of Acetone from Spectral Solvent Shifts
Authors: Abe Takehiro
Published: July 2006

This paper has presented the expression for the frequency shift, including the solvent refractive index and the dielectric constant; the expression has been determined on the basis of a previous paper (This Bulletin, 38, 1314 (1965)). According to the present theory and E. G. McRae’s theory (J. Phys. Chem., 61, 562 (1957)), the excited state dipole moment of acetone has been estimated to be 0.86 and 1.84 D respectively, both being smaller than the ground state value. The results calculated by the present theory show that the excited state polarizability is 163.1×10−25 cm3 and that the solvation energies in the solvents of n-heptane, cyclohexane, carbon tetra-chloride, ethyl ether, and methyl acetate are less in the ground states than in the excited states.
The Flotation of Cation by Cationic and Anionic Surfactants
Authors: Aoki Norichika , Sasaki Tsunetaka
Published: July 2006

The ion flotation of a cation by a cationic surfactant with the aid of an anionic chelating agent was studied for the system of Fe3+-ethylenediaminetetraacetic acid (EDTA)-octadecyldimethylammonium chloride (ODAC). The systems of Fe3+-EDTA and Fe3+-ODAC were also studied for purposes of comparison. The effects of the concentration of the above three components, the pH and the gas-flow time on the flotation efficiency were measured. The diagram of the flotation efficiency vs. the pH showed a W-shaped curve for the Fe3+-EDTA-ODAC system, which was explained by the formation of Fe3+-EDTA, Fe3+-ODAC and Fe3+-EDTA-ODAC complexes, each of which has a different optimum pH region of its formation. The flotation of a cation by an anionic surfactant was also studied using ferric, ferrous, silver and Malachite Green ions as cations and sodium dodecylsulfate (SDS) as an anionic surfactant. The flotation efficiency increased with the time of the gas flowing, except for the system of Fe3+-SDS. Such an increase was explained by the relatively insoluble nature of the corresponding SDS salts.
The Radiolysis of Aqueous Solutions of Potassium Iodide
Authors: Sawai Takeshi , Shinozaki Yoshiharu , Meshitsuka Gisuke
Published: July 2006

The radiolysis of potassium iodide aqueous solutions has been studied in order to elucidate the contribution of the hydrated electrons to the radiolysis mechanisms. The deaerated and aerated solutions were irradiated by 60Co γ-rays under various conditions, and the yields of iodine, hydrogen peroxide, hydrogen and oxygen were determined. The pH dependences of the initial yields of iodine and hydrogen peroxide in the deaerated solutions are different from the results obtained in the aerated solutions. These results can be reasonably explained by assuming the hydrogen atoms and hydrated electrons to be the reducing species. From an examination of the results, the radiolysis mechanisms of the potassium iodide aqueous solutions have been discussed. The rate constant of the reaction of hydrated electrons for iodine has been calculated to be 5.9×1010 M−1 sec−1.
The Liquid-Liquid Extraction of Alkaline Earth Metals with TTA (2-Thenoyltrifluoroacetone)
Authors: Akaza Ikuko
Published: July 2006

The liquid-liquid extraction of alkaline earth metals was investigated with a TTA-MIBK solvent and a NH4OAc-AcOH-NH4OH aqueous solution in the presence of relatively large amounts of the metals. The extractability of the metal ions was in the decreasing order of magnesium, calcium, strontium and barium, while their distribution ratios were too close to one another for them to be separated from each other. Critical studies were made on several factors affecting the distribution of each metal, such as the amount of metal in the aqueous solution, the concentration of TTA in the organic solvent, and the pH of the solution. It was noticed that the concentration of TTA in MIBK played a principal role in this extraction and that the logD-log(TTA) relation was shown as a curve, not a straight line. The relation in other similar cases had usually been shown as a straight line, but the new results were obtained by compensating pH-change, the extent of which was variable with the concentration of TTA in the system. Among the metal ions, calcium and magnesium could be separated from each other by carrying out the extraction from their solution in the presence of EDTA. A further extention of this extraction to a reversed-phase partition chromatography will be undertaken and reported on in another paper.
ON THE OXIDATION OF FERROUS HYDROXIDE BY AIR.—SUPPLEMENT
Authors: Miyamoto Susumu
Published: July 2006

(1) An interpretation on the real meaning of the observed oxidation velocity of ferrous hydroxide under the conditions of the author’s experiments was given to prevent misunderstanding of the author’s papers.

(2) The reason, why the experimental conditions, under which the author’s measurements were carried out, were adopted, was described.

(3) It was discussed that the oxidation velocity of ferrous hydroxide, observed by A. Krause under quite different conditions, will have quite a different meaning as that, observed by the author. The difference of the real meaning of the observed reaction velocity, caused by the difference of the experimental conditions, will explain why the effect of temperature, which was negligible under the author’s conditions, was found by A. Krause to be very great.
THE RADIOACTIVE CONSTITUENTS OF HOKUTOLITES AND OTHER MINERALS IN JAPAN
Authors: Yoshimura Jun
Published: July 2006

As to the uranium in hokutolite, there is no analytical evidence, hitherto, of its presence in this mineral, and it is thought quite useless to calculate it from the amount of radium, as the mineral is obviously of the secondary nature.

The radium- and thorium-contents of the two kinds of hakutoutes mentioned above are respectively of the same order and quite similar. The comparatively large content of radium, however, in comparison with the poorer content of thorium shows that the radioactivity of this mineral is mainly ascribed to radium and its disintegrating products and very little to the members of thorium-series.

It is seen that the allanite from Shirakawa, Kyoto Prefecture contains 1.05% Th O2 and 0.017% U3O8.

The uranium-content of the xenotime-portion of the xenotime-zircon from Ishikawa was determined to be 2.42% U3O8. According to K. Kimura(1), the average amount of uranium in the “ Kikukwa-seki” is said as being 1.92% U O2. These results indicate that the amount of uranium in the zircon-portion of the latter mineral is probably less than that in the xeno-time portion.

In conclusion, the author wishes to express his hearty thanks to Dr. S. Iimori for his kind direction during the course of this experiment.
Polarography of Lead-Arginine Hydrochloride Complexes
Authors: Lai Tsai-Teh , Chen Mon-Chao
Published: July 2006

The complexation of lead ion with arginine hydrochloride has been studied polarographically at 30°C. Four kinds of complex species, PbCl+, Pb(H2Arg)Cl2+, Pb(H2Arg)(OH)2+ and Pb(H2Arg)2(OH)3+ (where H2Arg denotes the arginine univalent cation) were confirmed in various pH range, respectively. The logarithmic dissociation constant of Pb(H2Arg)2(OH)3+ was found to be 10.33±0.03 at ionic strength 0.9.
Tropylation of Azulene, 1-Oxaazulan-2-one, and Their Derivatives, and Electrophilic Reactions of the Tropylazulene Derivatives
Authors: Nozoe Tetsuo , Toda Takashi , Asao Toyonobu , Yamanouchi Akira
Published: July 2006

The tropylation of azulene, oxaazulan-2-one, and their derivatives was investigated, and various 1 and/or 3-tropylazulenes and 3-tropyloxaazulan-2-ones were obtained. The NMR, UV, and visible spectra of these tropylazulenes were then discussed. Some electrophilic reactions, such as azo-coupling and the acid treatment of four kinds of tropylazulenes, were studied, and it was found that exchanges of the tropyl group and the attacking electrophilies occurred.
Studies on Heteroaromaticity. XXI. 1,3-Dipolar Cycloaddition of N-Phenyl-C-(6-uracilyl)nitrone
Authors: Sasaki Tadashi , Ando Moriyasu
Published: July 2006

N-Phenyl-C-(6-uracilyl)nitrone (II) was prepared in 80% yield from orotaldehyde (I) and phenylhydroxylamine. II underwent 1,3-dipolar cycloaddition reactions with several ethylenic and acetylenic compounds to afford the corresponding isoxazolidines (IIIa—f) and isoxazolines (IVg—i). Similar reactions of II with phenyl isocyanate, carbon disulfide and with enamine were carried out successfully. The structural elucidation of these products was done on the basis of their NMR spectra.
The Reaction Products of the Hydroformylation of Acrolein Acetals and Acetates
Authors: Maeda Itsutoshi , Yoshida Ryonosuke
Published: July 2006

The hydroformylation reactions of acrolein acetals and acetates were carried out in order to discuss the side reactions and any subsequent reactions. Acrolein cyclic acetals reacted with carbon monoxide and hydrogen in the presence of a dicobalt octacarbonyl catalyst to give n- and iso-aldehydes in a 2:1 ratio; they gave no further reaction products. Acrolein diethylacetal underwent hydroformylation using a rhodium catalyst to give n- and iso-aldehydes in a 1:2 ratio. In the presence of a cobalt catalyst, however, various products were obtained. As a result of the acidity of cobalt hydrocarbonyl and a high reaction temperature, n-aldehyde, first formed in benzene, underwent change to 2,5-diethoxytetrahydrofuran and 1,1,4-triethoxybutane. In ethanol, n- and iso-aldehydes gave the corresponding acetals. In the hydroformylation of acrolein acetate, only n-aldehyde was obtained. Iso-aldehyde seemed to be converted into 2-methyl-3-acetoxyacrolein by deacetylation. In ethanol, besides n-acetal, iso-acetal and propionaldehyde acetate, 2,5-diethoxytetrahydrofuran and 2-methyl-3-ethoxyacrolein were recognized. The former seemed to be formed from n-aldehyde by ring closure and ethanolysis. The latter seemed to be formed by the ethanolysis of 2-methyl-3-acetoxyacrolein. In ethyl orthoformate, no side reaction was observed and the yield of the main product, 1,1-diacetoxy-4,4-diethoxybutane, amounted to 80%.
The Electrophilic Substitution Reactions of 2-Aminotropone and Its N-Alkyl Derivatives
Authors: Nozoe Tetsuo , Ryu Shoji , Toda Takashi
Published: July 2006

The electrophilic substitution reactions of 2-aminotropone (I), 2-methylaminotropone (II), and 2-dimethylaminotropone (III) were investigated. The structure of the products was proved by hydrolysis to lead to known tropolone derivatives. By the nitrosation of II, N-nitroso-2-methylaminotropone was obtained in a good yield; this compound is a new type of active troponoid compound. The substitution reactions of III gave tropolone derivatives, accompanied by the hydrolysis of the dimethylamino group. The mechanism of the hydrolysis is then discussed.
Electrolytic Reduction of Naphthalene in Various Alcohol-Hexamethylphosphoramide Systems
Authors: Asahara Teruzo , Sen\={o} Manabu , Kaneko Hideaki
Published: July 2006

The electrolytic reduction of naphthalene was carried out in various alcohol-hexamethylphosphoramide (HMPA) systems in the presence of lithium chloride. The reduction of naphthalene proceeds effectively at relatively low cathode potentials in the presence of HMPA; the composition of the products varies with the changes in the reduction potential, the kind of alcohols, and the concentration of HMPA. The dark blue color is observed at the cathode during the electrolysis in HMPA solutions in either the presence or the absence of ethanol. It is suggested that the color reflects the generation of solvated electrons, and that reduction of naphthalene is caused not through a direct electron-transfer from the cathode, but through a reaction with solvated electrons as the reductive agent.
Reactions of Vinyloxyboranes. A Convenient Method for the Preparation of β-Hydroxy Thiolesters, Esters and Ketones
Authors: Inomata Katsuhiko , Muraki Masayoshi , Mukaiyama Teruaki
Published: July 2006

It was found that the reaction of thioboronites with carbonyl compounds and ketene proceeds with the initial formation of vinyloxyboranes (VII). The boranes were found to be important intermediates for the formation of β-hydroxythiolesters by the reaction with various carbonyl compounds. Vinyloxyborane derivatives can be alternatively prepared by the reactions of trialkylboranes and α-diazocarbonyl compounds. The boranes similarly reacted with carbonyl compounds to give β-hydroxyketones and β-hydroxyesters.
Studies of the Synthetic Model Enzyme. The Synthesis of Cyclo(His–Glu–Cys-d-Phe–Gly)2 as the Esterase Model
Authors: Nakajima Kiichiro , Okawa Kenji
Published: July 2006

To study the mechanism of enzyme action, cyclo(His–Glu–Cys-d-Phe–Gly)2 was prepared as an esterase model from the corresponding linear decapeptide by the azide methods. The esterase-like activity of this cyclic decapeptide in reaction to p-nitrophenyl acetate was three times greater than that of the linear decapeptide, the curve of the catalytic coefficient versus the different pH is of a bell type, and the optimum pH was recorded at about 7.6. The kinetics of the hydrolysis obeyed Michaelis-Menten’s typical equation.