bluuebunny/crossref_metadata_2025 huggingface dataset:
Transformation of Progesterone by Aspergillus niger 100 and Rhizopus nigricans REF, 129
Authors: Sallam Lotfy , El-Refai Abdel-Monem , El-Kady Ismail
Published: July 2006

The microbiological transformation of progesterone by the local moulds Aspergillus niger and Rhizopus nigricans was studied. To a 48 hr old culture, progesterone (0.4 g/l medium) dissolved in ethanol was added and the transformation was left to proceed for 72 hr. Thereafter, the different transformation products were resolved chromatographically. The identity of each product was established through the determination of mp, mixed mp, optical rotation and ultraviolet as well as infrared absorption spectra. A comparison of the Rf values of each product with that of the corresponding reference using different solvent systems as well as their colours with two spray reagents was used as a further proof for the identity of the isolated products. In case of A. niger, progesterone was converted to 17α-hydroxyprogesterone; 21-hydroxyprogesterone (cortexone); 11α-hydroxyprogesterone; 11α,17α-dihydroxyprogesterone; 6β,11α-dihydroxyprogesterone and 11α, 17α, 21-trihydroxyprogesterone (epicortisol). These products together with 11α-hydroxy-5α-pregnane-3,20-dione were also identified in case of R. nigricans.
The Radiolysis and Photolysis of Methanolic Solutions of Eosin. I. The γ-Radiolysis of Neutral and Alkaline Solutions
Authors: Kimura Kazuie , Miwa Takuji , Imamura Masashi
Published: July 2006

The γ-radiolysis of eosin has been studied in deaerated neutral and alkaline methanolic solutions. Eosin is reduced principally with CH2OH radicals in dilute solutions. In neutral solutions, G(–eosin) is about 2 at the eosin concentration of 10−5m and increases as the concentration of eosin is increased. The final products are leuco-eosin and an unidentified substance which has an absorption peak at 455 nm. In an alkaline solution (10−5m), G(–eosin) is about 4 and the product is semireduced eosin, which is stable in the dark and which undergoes photo-debromination. The ESR spectrum of semireduced eosin has also been recorded. Comparative studies have also been made on uranin solutions.
Thermodynamic and X-Ray Studies of Solid Solutions of Silver Bromide and Lithium Bromide
Authors: Tsuji Toshihide , Murakoshi Shunichi , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

A miscibility gap in AgBr-LiBr solid solutions has been found by the high temperature X-ray diffraction method, and a new phase diagram is presented. Activity, partial molar free energy, enthalpy and entropy of AgBr in AgBr-LiBr solid solutions have been obtained at 350 and 400°C from the e.m.f. data of galvanic cells of the type Ag/AgBr-LiBr/Br2. It has been found that the solid solution forms a regular solution dinned by Hildebrand.
The Photochromism, Thermochromism, and Piezochromism of Dimers of Tetraphenylpyrryl
Authors: Maeda Koko , Chinone Akiko , Hayashi Taro
Published: July 2006

By the oxidation of tetraphenylpyrrole, two types of dimers of tetraphenylpyrryl were obtained. One dimer showed piezochromism and thermochromism, while the other showed photochromism and thermochromism. These phenomena were found to correspond to those of the piezochromic and photochromic dimers of triphenylimidazolyl obtained from triphenylimidazole. The photochromism, thermochromism, and piezochromism of the dimers of tetraphenylpyrryl are determined to be due to the radical dissociation caused by irradiation, heating, and grinding, the same machanism as that in the case of the dimers of triphenylimidazolyl.
β-Ferrocenyl-α,β-unsaturated Ketones. III. The Conformational Study of β-Ferrocenyl-α,β-unsaturated Ketones by Means of IR Spectroscopy
Authors: Kono Hiromichi , Shiga Mikio , Motoyama Izumi , Hata Kazuo
Published: July 2006

The geometrical and conformational isomerism of various β-ferrocenyl-α,β-unsaturated ketones, most of which had been reported in a previous paper, was discussed on the basis of their IR spectra in the 1700–1600 cm−1 range and their NMR spectra. An unusually strong IR absorption of the olefinic double bond was observed in comparison with that of the carbonyl group. Considering the IR and NMR data, it was concluded that 3-ferrocenyl-1-(p-substituted phenyl)-2-propen-1-ones may mostly exist in a s-cis conformation.
Effect of Carbonyl Compounds on Polymerization by Metal Acetylacetonates
Authors: Kaeriyama Kyoji
Published: July 2006

Some ketones and aldehydes have an accelerative effect on the polymerization of various monomers by various metal chelates of acetylacetone. The conversion increases with an increase in the concentration of these additives in a correspondingly increasing polymerization time. A radical is formed by the equimolar reaction of cyclohexanone and manganese (III) acetylacetonate and by the reaction of two aldehyde molecules and a molecule of the chelate. The , order with a monomer is lowered from 1.64 to 1.13 and to 1.07 by the addition of cyclohexanone and caproic aldehyde respectively. The relation between the polymerization rate and the square root of the chelate concentration is linear without any additive ; concave and convex curves are obtained for the systems containing cyclohexanone and caproic aldehyde respectively. The apparent activation energy is lowered from 19.9 kcal/mol to 13.9 and to 14.3 in the presence of cyclohexanone and caproic aldehyde respectively. The effectiveness of ketones is dependent on the nucleophilicity. A mechanism of the initiation reaction which interprets the molar ratio of reactants, the kinetical parameters, and the spectral data is proposed.
Homolytic Chlorination of Aliphatic Compounds. IV. Chlorination of Chloroalkanes by t-Butyl Hypochlorite
Authors: Kosugi Masanori , Takeuchi Kohji , Migita Toshihiko
Published: July 2006

Chlorination of chloroalkanes by t-butyl hypochlorite was investigated by means of competitive experiment. Relative reactivities thus obtained were compared with those toward hydrogen abstraction by t-butoxy radicals derived from other sources. From the results it was concluded that a main chain carrier of this chlorination was a t-butoxy radical. Structure-reactivity relationships in t-butyl hypochlorite chlorination were also investigated. Linear free energy relationship was found to exist between the reactivities of methyl hydrogen of CH3-X and Taft’s σ* constants for the substituent X,ρ*=−0.69. α-Chlorine substituents were found always to enhance the rate of hydrogen abstraction of this position. Resonance effects of a-chlorine substituent is considered to be more important than in photochlorination with chlorine.
Hydrogen-bonding Effects on the Electron Spin Resonance Spectra of the Anion Radicals of Several Aromatic Amine N-Oxides
Authors: Kubota Tanekazu , Oishi Yoshiko , Nishikida Koichi , Miyazaki Hiroshi
Published: July 2006

The hydrogen-bonding effects of ethanol, phenol, and water on the electron-spin-resonance spectra of the anion radicals of 4-nitro- and 4-cyano-pyridine N-oxides, pyrazine mono- and di-N-oxides, and 4-nitropyridine electrochemically generated in dimethylformamide have been studied quantitatively. The equilibrium constant, K, pertinent to the hydrogen-bonding systems was determined on the basis of analyses of the variation in the hyperfine coupling constant caused by the addition of a proton donor. The active site in a radical anion participating in the hydrogenbonding interaction and the K values were then discussed on the basis of the theoretical calculation of the spin density and the coupling constant of the radicals in the hydrogen-bonding interaction. It has been pointed out that this sort of experiment in hydrogen bonding interaction is also useful for assigning the hyperfine coupling constant to a definite atom in a radical. Last, these K values are used to explain the mechanism of radical formation by the controlled potential electrolysis at different reduction potentials of pyrazine mono- and di-N-oxides in dimethylformamide-ethanol mixed solvents.
Semi-Empirical SCF MO Method for Systems Including All Valence Electrons
Authors: Hirota Fumihiko , Nagakura Saburo
Published: July 2006

For the purpose of evaluating approximate SCF-MO’s for systems including all valence electrons, two semi-empirical methods are presented. One of them (method I) uses non-empirical Coulomb integrals and the other (method II) empirical ones. The orbital energies, charge distributions, and excitation energies are calculated for ethylene, acetylene formaldehyde, carbon monoxide and hydrogen cyanide, and are compared with those obtained by the other semi-empirical and non-empirical calculations and also with the corresponding experimental values. The present methods are found to give rather satisfactory results. The calculated orbital energies are improved by the present methods compared with those by the CNDO type calculation. Calculated charge distributions are well coincident with those of the non-empirical SCF calculation. Calculated dipole moments change in parallel with experimental values from a molecule to another, though the former values are generally larger than the latter.
Reactions of Various Thione-compounds with Epoxides. A New Method for the Transformation of the C=S Bond into the C=O
Authors: Ueno Yoshio , Nakai Takeshi , Okawara Makoto
Published: July 2006

The reactions of propylene oxide (PO) with various thione-compounds containing two α-hetero atoms including dithiocarbamates, thioncarbamates, trithiocarbonates and thioureas, and their cyclic analogs were studied in the presence of triethylamine or boron trifluoride etherate as a catalyst. It was found that most of these thione-compounds reacted with PO at 170–180°C to afford the corresponding one-compounds in good yields. This type of reaction may provide a new method for the transformation of the C=S bonds in thione-compounds into the C=O bonds. Boron trifluoride etherate appeared to be more effective than triethylamine as the catalyst. The mechanism which involves initial cycloaddition of PO to the C=S bond followed by elimination of propylene sulfide was proposed for the transformation. The reactivities of these thione-compounds were significantly affected by whether they are cyclic or open-chain and by the nature of the α-hetero atoms: the cyclic thione-compounds were more reactive then the open-chain analogs except for a pair of thioureas and the enhancement by the α-hetero atoms was in the order: N,O≈N,N>N,S>S,S. Both observations may be interpreted in terms of basicity of the thione-compounds. These results also support the proposed mechanism for the formation of 2-oxazolidones from 2-substituted imino-1,3-dithiolanes with epoxides in our preceding paper.
Location of Gadolinium Ions in Hydrated Oxalate by ESR
Authors: Chi Hsiu
Published: July 2006

Gadolinium oxalate hydrate crystallizes isomorphously as La2(C2O4)3·10H2O, with two molecules in a unit cell of dimensions: a0=11.61+0.05, b0=9.656+0.020, c0=10.22+0.05 Å and β=119.0+0.1°. A detailed study of the d-spacings for the coprecipitates of varying composition in the La-Gd oxalate system was made, and 46 nearest-neighbor pairs were selected for Van Vleck second moment calculation. Agreement of the results of the calculation with those of the experiment justifies the suggested model representing the location of the gadolinium ions in the hydrated oxalate salt.
The Polymerization of α-Amino Acid N-Carboxy Anhydride (4-Alkyl-oxazolidine-dione). IV. A Novel Synthesis of a Block Copolypeptide
Authors: Oya Masanao , Uno Keikichi , Iwakura Yoshio
Published: July 2006

It has been found that, when the polymerization of NCA is initiated with n-butylamine in acetonitrile, the amino end group in the polymer produced which is insoluble in the solvent is active (Y. Iwakura, K. Uno and M. Oya, J. Polym. Sci., Part A-1, 8, 2165 (1968)). The amino end group in the polymer isolated without drying could initiate the polymerization of NCA in acetonitrile. By using this characteristic of the polymer, block copolypeptides consisting of various kinds of α-amino acid and of various chain lengths were synthesized. The solubility of the block copolypeptides in a solvent was different from that of the random copolypeptides obtained by the usual copolymerization of a mixture of NCA in acetonitrile. Sometimes the infrared spectra of the block copolypeptides were different from those of the random copolypeptides.
Asymmetric Hydrogenation of C=N Double Bond with Modified Raney Nickel 1. New Determination Method for the Reaction Mechanism Using Asymmetric Catalyst
Authors: Izumi Yoshiharu , Takizawa Hidemitsu , Nakagawa Kunio , Imamura Ryushichi , Imaida Masami , Ninomiya Toshio , Yajima Shinichi
Published: July 2006

The hydrogenation process of ethyl 2-acetoximinopropionate was investigated by means of a novel technique using asymmetric hydrogenation with an asymmetrically modified R–Ni catalyst. It was found that the hydrogenation of ethyl 2-acetoximinopropionate to ethyl alaninate proceeded in two steps through ethyl acetoxyalaninate, and that the asymmetric hydrogenation was performed in the step of the formation of ethyl acetoxyalaninate from ethyl 2-acetoximinopropionate. Besides, the asymmetric reductive amination of ethyl pyruvate was tested with an asymmetrically modified R–Ni catalyst.
Reaction of Sulfoxides with Acylating Reagents. IV. The Catalytic Effect of Both the Brönsted and Lewis Acids in the Oxygen Exchange Reaction of Diaryl Sulfoxides with Acetic Anhydride
Authors: Kise Masahiro , Oae Shigeru
Published: July 2006

Diaryl sulfoxides undergo oxygen exchange and racemization reaction with acetic anhydide. The rate of racemization of p-tolyl phenyl sulfoxide was found to be twice that of oxygen exchange. The remarkably small substituents effect is also in keeping with the SN2 type mechanism. Addition of acetic acid increases the rate of both the racemization and oxygen exchange. Racemization of sulfoxides is also known to be catalyzed markedly by a small amount of Lewis acid. When the reaction was carried out in the presence of a small amount of both acetic acid and Lewis acid, the ratio of the rate constants, kex⁄krac becomes unity. This may mean that the presence of both Brönsted and Lewis acids facilitates the cleavage of S–O bond by easy protonation (or hydrogen-bonding) or coordination on the sulfoxide oxygen, and the assistance of the nucleophilic attack by acetate becomes less important in the reaction. The larger substituent effect is also in keeping with the SN1 type mechanism.
The Rearrangement of Chromanone Oximes with Lithium Aluminum Hydride
Authors: Ito Shoei
Published: July 2006

The lithium aluminum hydride reduction of 7-methoxychromanone oxime (I) and 7-methoxy-3-methylchromamone oxime (II) gave only the rearrangement product (the 2,3,4,5-tetrahydro-1,5-benzoxazepine derivative). 7-Methoxy-2-methylchromanone oxime (III) and 7-methoxy-2-isopropylchromanone oxime (IV) gave a mixture of the rearrangement product (secondary amine) and the normal reduction product (primary amine). 7-Methoxy-2-t-butylchromanone oxime (V) gave only the normal reduction product. The main conclusions to be drawn from these results are as follows: (1) The chromanone oximes without a C2 substituent give only the rearrangement product. (2) The chromanone oximes with a C2 substituent give a mixture of the normal reduction product and the rearrangement product. (3) The more bulky substituent at C2 gives the more normal reduction product and the smaller quantity of the rearrangement product.
Aminocyclitols. XXII. A Synthesis of Actinamine and Hyosamine
Authors: Suami Tetsuo , Ogawa Seiichiro , Sano Hiroshi
Published: July 2006

Hydrazinolysis of 2,4,5,6-tetra-O-acetyl-1,3-di-O-p-toluenesulfonyl-myo-inositol, followed by catalytic hydrogenation afforded myo-inosadiamine-1,3 via an intermediary 6,7-diazabicyclo[3.2.1]-octane-2,3,4,8-tetrol. In this reaction, the use of N,N′-dimethylhydrazine and N-methylhydrazine, instead of hydrazine, gave actinamine: a component of an antibiotic spectinomycin, and N-methyl-myo-inosadiamine-1,3: an important intermediary compound for a synthesis of Dl-hyosamine, respectively. Details of the convenient syntheses of actinamine and Dl-hyosamine are described.
The Crystal and Molecular Structure of Demycarosyl Leucomycin A3 Hydrobromide
Authors: Hiramatsu Mikio , Furusaki Akio , Noda Toshiharu , Naya Keizo , Tomiie Yujiro , Nitta Isamu , Watanabe Tetsuo , Take Teruo , Abe Jinnosuke , Omura Satoshi , Hata Toju
Published: July 2006

The stereochemically-complete molecular structure of demycarosyl leucomycin A3, C30H49-NO11, has been determined by means of an X-ray crystal analysis of its hydrobromide. The crystals of the hydrobromide are orthorhombic with four chemical units in a unit cell with the dimensions of a=19.52±0.03, b=20.63±0.03, and c=9.28±0.03 Å. The space group is P212121. As a result of the present study, it has been found that the crystals contain about 0.6 mole of ethanol per mole of the hydrobromide as alcohol of crystallization. The intensity data were obtained from equi-inclination integrating Weissenberg photographs taken with CuKα radiation around the b and c axes. The structure was elucidated by means of the minimum function, least-squares, and Fourier methods. The atomic coordinates obtained were refined by the block-diagonal least-squares method, anisotropic thermal motion being assumed for only the bromine atom. The final R factor is 14.6%. The molecular structure thus obtained corresponds exactly to that proposed in 1967 by Hata et al. on the chemical evidence, considering the allylic rearrangement in the hydrolysis of leucomycin A3 with dilute hydrochloric acid. The conjugated diene system in the macro ring has the trans-trans configuration. The sugar component, mycaminose, forms a β-glycosidic linkage with the lactone ring.
Crystal Structure of Fukinolidol Di-Bromoacetate
Authors: Katayama Chuji , Furusaki Akio , Nitta Isamu , Hayashi Mitsuo , Naya Keizo
Published: July 2006

Fukinolidol di-bromoacetate, C19H24O6Br2, is a derivative of the new sesquiterpenoids isolated from the flower stalks of wild butterburs. The crystal of this derivative is monoclinic, with two molecules in a unit cell with dimensions of a=17.13, b=8.21, c=7.59 Å, and β=98.8°, and with the space group P21. The structure was elucidated by the heavy-atom method, and the absolute configuration was determined by the application of the anomalous dispersion effect of bromine. The atomic parameters were refined by the least-squares method, using a block-diagonal approximation. The structure thus obtained is the same as that shown by the organic chemical investigation which was carried out parallel with the present X-ray analysis. The molecule has a novel bicyclononane structure with a cis-fused system of a five-membered and a six-membered ring; it also has a spiro γ-lactone ring connected to the former ring. The lactone ring is almost planar, and the other five-membered ring takes a typical envelope conformation, while the six-membered ring is of the chair form.
Effect of Some Metal Oxides on the Specific Resistivities of Magnesium Oxide
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The specific resistivities of magnesium oxide prepared by igniting magnesium hydroxide at about 1700°C were investigated in the temperature range 200–1200°C. The magnesium oxide was found to have a p-type character by the thermoelectric power method. Ignition at 1000°C in an oxygen stream brought about a small increase in specific resistivities, whereas ignition in a vacuum of 10−3 mmHg caused no appreciable change. The sample including univalent-metal oxides such as Na2O or Li2O showed a distinct decrease in specific resistivities and was converted from a p-type to an n-type semiconductor. Addition of tervalent-metal oxides such as γ-alumina or B2O3 to the magnesium oxide, however, raised the resistivities but gave no change in type.
Structure and Intramolecular Motions in Bicyclo[2.2.2]octane as Studied by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo , Morino Yonezo
Published: July 2006

A least-squares analysis of the electron-diffraction intensities for bicyclo[2.2.2]octane in gas phase measured at 28°C has given the following structural parameters: rg(C–C) (average)=1.542±0.004Å, rg(C–H) (average)=1.107±0.009Å, rg(C1–C2)=1.538±0.015Å, rg(C2–C3)=1.552±0.029Å, ∠C1–C2–C3=109.7°±0.7°, and ∠H–C–H=110·1°±5·6°, where the uncertainties represent estimated limits of error. The potential function for the twisting motion around the D3h symmetry axis is found to have a broad minimum; in terms of the dihedral angle of torsion about the C2–C3 axis, φ, the potential has an rms angle of 12.0°±1.5° and a “classical turning point” of 21.5°±0.5° (7.2° and 12.8°, respectively, in terms of the dihedral angle of twist, τ). Best fit to the observed intensities has been achieved when a quartic function, V(φ)=k2φ2+k4φ4 with k2=−4.0 kcal/mol and k4=54.2 kcal/mol, is assumed. The potential function probably has a hump of the order of 100 cal/mol at the D3h conformation. Hence, this molecule may be regarded as having a “quasi-D3h structure”. The above features are consistent with those for the derivatives of this molecule in crystal phase studied by Dunitz and Ermer by X-ray diffraction, and also with semiempirical estimates based on the calculations of the intramolecular strain energy.
Polarography of Halides in Dimethylformamide. IV. The Stability Constants of the Halo Complexes of Mercury (II)
Authors: Matsui Yoshihisa , Date Yoshio
Published: July 2006

The overall stability constants (β) of mercuric halide and the tri- and tetrahalogenomercurate ions in dimethylformamide containing 0.1 m tetraethylammonium perchlorate were evaluated by the polarographic method at 25°C. The values of log β obtained were: 24.16 for HgCl2, 31.23 for HgCl3−, 34.57 for HgCl42−, 24.17 for HgBr2, 31.62 for HgBr3−, 34.73 for HgBr42−, 25.93 for HgI2, 33.34 for HgI3−, and 36.02 for HgI42−.
The Syntheses and Properties of the Complexes of Boron with Ethylenediaminetetraacetic Acid and Its Analogs
Authors: Nakatani Mitsuhisa , Takahashi Yoshiaki , Ouchi Akira , Watanuki Kunihiko
Published: July 2006

Two compounds of boron with ethylenediaminetetraacetic acid, H6EDTA(BF4)2 and H4EDTA-(BF3)2, as well as complexes with cyclohexanediaminetetraacetic acid and nitrilotriacetic acid, have been synthesized. Their properties, including their infrared and ultraviolet spectroscopic data, have been investigated and discussed.
On the Polarographic Limiting Current of Solubilized Dye in Nonionic Surfactant Solutions
Authors: Hayano Shigeo , Shinozuka Noriko
Published: July 2006

The nature of the limiting current of the reduction of solubilized dye with nonionic surfactants on a mercury-drop electrode was examined. The solution of anthraquinone derivatives solubilized in an aqueous solution of a nonionic surfactant showed a proportionality of the limiting current to the dye concentration. The linear dependence of the current on the square-root of the mercury-column height, the solpe of the log-plot, and the i-t curves indicated the limiting current to be diffusion-controlled. From the i-t curve measurements, the acceleration of the instantaneous current at the end of the mercury-drop growth was observed with the polyoxyethylene nonylphenylether and Triton X-100. This can be interpreted in relation to the reorientation of the surfactant molecules.
Synthesis of 1,3-Thiazine Derivatives from 2-Iminocyclo-pentanedithiocarboxylic Acid
Authors: Muraoka Motomu , Yokoyama Masataka , Yamamoto Kiyoko , Takeshima Tatsuo
Published: July 2006

Several new 3-substituted and 3,3-disubstituted-1,3,4,5,6,7-hexahydro-1-thioxocyclopenta[d]-[1,3]thiazines were obtained by the reactions of 2-iminocyclopentanedithiocarboxylic acid with some aldehydes and ketones. Some intermediate compounds in these reactions such as 2-amino-2-[2-(piperonylidenamino)-1-cyclopenten-1-yl]thiocarbonylthiocyclopentanedithiocarboxylic acid, 2-amino-2-[2-(vanillylidenamino)-1-cyclopenten-1-yl]thiocarbonylthiocyclopentanedithiocarboxylic acid, and 2-amino-2-[2-(4-methoxybenzylidenamino)-1-cyclopenten-1-yl]thiocarbonylthiocyclopentanedithiocarboxylic acid could be isolated.
Geometric Configurations of α-Cyano-β-methyl-β-alkylglycidic Esters
Authors: Igarashi Minoru , Akano Makiko , Fujimoto Akira , Midorikawa Hiroshi
Published: July 2006

α-Cyanoglycidic ester derivatives have been prepared from alkylidenecyanoacetic esters with hydrogen peroxide. The NMR technique has been applied to the study of the geometric configurations of the stereoisomeric mixture of the glycidic esters. It has been found that the β-methyl protons cis to the ester group respond at a higher field than do the trans protons.
The Preparation of α-Amino-α-benzylmercaptopropionic Acid Derivatives
Authors: Kaneda Akira , Sudo Rokuro
Published: July 2006

The preparation of N-acyl derivatives of α-amino-α-benzylmercaptopropionic acid was investigated. It is described that pyruvic acid was treated with amides to afford N-acyl-α-amino-α-hydroxypropionic acids, which were then substituted into N-acyl-α-amino-α-benzylmercaptopropionic acids. In another experiment, Steglich’s method was improved in order to afford three N-acyl derivatives of α-amino-α-benzylmercaptopropionic acid in a better yield.
The Characterization of Malloprenol and Its Ester with Linolenic Acid Isolated from the Leaves of Mallotus japonicus
Authors: Noda Toshiharu , Take Teruo , Watanabe Tetsuo , Abe Jinnosuke
Published: July 2006

An isoprenoid alcohol (I) and the ester with linolenic acid (II) isolated from Mallotus japonicus of Euphorbiaceae were investigated. The trivial name “mallophenol” was proposed to describe the prenol (I). Nuclear magnetic resonence studies showed that the prenol contained one trans and six cis internal isoprene residues, and a cis ‘OH-terminal’ isoprene residue.
The Catalytic Dehydrogenation, Dehydroxylation and Dehydroxymethylation of Benzyl Alcohol. I. The Scope and the Kinetic Study
Authors: Ishige Masayoshi , Sakai Koji , Kawai Masatoshi , Hata Kazuo
Published: July 2006

Benzyl alcohol was dehydrogenated to benzaldehyde when it was heated in the presence of various metal catalysts. It was found that the dehydrogenation was accompanied by a reductive dehydroxylation and dehydroxymethylation which led to the production of toluene and benzene respectively. The compositions of the products, which mainly consisted of benzaldehyde, toluene, and benzene, were greatly affected by the chemical nature of the catalysts used. The results of the reactions in a sealed tube or in an authoclave suggested that a pseudo-equilibrium between benzyl alcohol and benzaldehyde was attained during the reaction in a closed system. The formation of CO2, CH4, and other hydrocarbons as gaseous products was also observed. From these results, the catalytic dehydrogenation, dehydroxylation, and dehydroxymethylation were assumed to proceed competitively via a certain metal benzyl complex which is formed as an adsorbed transition complex upon the catalyst metal.
The Hydroformylation of Nitroalkenes with Rhodium Carbonyl
Authors: Takesada Masahiko , Wakamatsu Hachiro
Published: July 2006

The hydroformylation of butenes in nitrobenzene or nitroethane gives C5-aldehydes in an excellent yield in the presence of tetrarhodium dodecarbonyl, but in only a poor yield in the presence of dicobalt octacarbonyl. Under hydroformylation conditions, nitrobenzene is hydrogenated to aniline above 150°C with rhodium carbonyl and at 125°C with cobalt carbonyl. The hydroformylation of nitroalkenes with rhodium carbonyl is described. 4-Nitrostyrene gives isomeric (4-nitrophenyl)-propionaldehydes in a 96% yield. 3-Nitropropene-1 gives C4-nitroaldehydes, mostly 2-methyl-3-nitropropionaldehyde, in a 96% yield. However, no reaction of nitroethylene occurred below 140°C.
Studies of Peptide Antibiotics. XX. Synthesis of Tyrocidine B
Authors: Kuromizu Kenji , Izumiya Nobuo
Published: July 2006

A cyclic decapeptide, cyclo-(l-Trp-d-Phe-l-Asn-l-Gln-l-Tyr-l-Val-l-Orn-l-Leu-d-Phe-l-Pro-) (XVIII), having the amino acid sequence of natural tyrocidine B has been synthesized, p-Methoxybenzyloxycarbonyl-Trp-d-Phe-OH was transformed into an acyldipeptide hydroxysuccinimide ester by reagents of hydroxysuccinimide-dicyclohexylcarbodiimide, and the acyldipeptide ester obtained was coupled with a neutral octapeptide. An acyldecapeptide acid thus obtained was subjected to the cyclization reaction. The antibacterial activity of the synthetic product (XVIII) toward Gram positive microorganisms is found to be nearly the same as that of synthetic tyrocidine A, indicating that the l-phenylalanine residue in tyrocidine A can be replaced by l-tryptophan without causing decrease in activity.
Preparation of 1,4-Cycloalkanediones by Hypoiodite Oxidation of Cycloalkanols
Authors: Mori Takasi , Matsui Kiyohide , Nozaki Hitosi
Published: July 2006

Lead tetraacetate oxidation of 11, 12 and 13-membered cycloalkanols gives improved yields of 2,5-polymethylenetetrahydrofurans II in the presence of iodine. Oxidative cleavage of II furnishes 1,4-cycloalkanediones VII.
Dielectric Relaxation and Molecular Structure. II Dielectric Relaxation in Dibutyl Ether, Diphenyl Ether and Benzophenone in Various Nonpolar Solvents
Authors: Vij J T , Srivastava K K
Published: July 2006

Measurements of dielectric constant and loss have been made at 1 Mc and 9.44 GHz for dibutyl ether and benzophenone in various solvents, e.g., n-heptane, benzene, cyclohexane, carbon tetrachloride, decalin and Nujol. Whereas, diphenyl ether has only been studied in benzene and cyclohexane. The values of relaxation time and distribution parameter have been determined by using Cole-Cole’s equation in terms of the so-called slopes, a0, a′, a″ and a∞. The relaxation time values show a regular increase with the increase in viscosity of the medium both for dibutyl ether and benzophenone. The observations seem to suggest that dibutyl ether relaxes both by molecular and intramolecular mechanisms. The dipole moments in various solvents have also been calculated.
Studies of Photochemical Reactions Using Organic Photosensitizers. I. Benzene-Photosensitized Decomposition of Nitrous Oxide
Authors: Yamashita Shigeru , Adachi Kin-ichi , Hayakawa Teruo
Published: July 2006

Benzene-photosensitized decomposition of nitrous oxide has been studied in a mercury-free reaction system. 2537 Å line of low-pressure mercury lamp was absorbed by benzene and the excitation energy of benzene was transferred to nitrous oxide by triplet-triplet energy transfer mechanism. Only N–O bond rupture of nitrous oxide has been observed, which is reasonable from energetic view point. The decomposition yield of the excited triplet state of nitrous oxide was estimated to be 15% and the triplet state seems to be less than 84 kcal/mol above the ground state.
The Reactions of Propylene-1,3,3,3-d4 Photosenitized by Hg(3P1), Cd(3P1), and Benzene-h6 and -d6
Authors: Hirokami Shun-ichi , Sato Shin
Published: July 2006

A comparative study has been made of the reactions of cis- and trans-propylene-1,3,3,3-d4 photosensitized by benzene-h6 and -d6 and by Hg(3P1) at room temperature and by Cd(3P1) at 275°C. The main reaction observed in every photosensitization was a cis-trans isomerization; no isomerization to propylene-2,3,3,3-d4 was observed under the conditions employed. This is in marked contrast to the isomerization of ethylene-d2. The ratio of cis- to trans-propylene-1,3,3,3-d4 after prolonged irradiation was unity. The decomposition observed in the mercury photosensitization was also studied in detail; its quantum yield was less than one-tenth that of the cis-trans isomerization. The material balance between the decrease in the reactant and the amount of the products was well preserved, but the energy balance between the absorbed photons and the quantum yield of products was not preserved at pressures below 150 Torr. A possible mechanism is discussed.
Effect of Halogenation on Intramolecular Energy Transfer in Rare Earth Chelates
Authors: Morita Makoto , Shionoya Shigeo
Published: July 2006

Using tris-dibenzoylmethanates of terbium(III) and other rare earths(III) we investigated the effect of halogenation of the central hydrogen of a 1,3-diketonate ligand on the luminescence properties of these chelates in rigid media. As a result of halogenation, all chelates display blue shift of the ligand phosphorescence, the intensity of the rare earth emission IRE relative to that of the phosphorescence Iph is markedly decreased in the order of H→Cl→Br, and the lifetime of the phosphorescence τph decreases in the same order. These facts provide the evidence that the intramolecular energy transfer takes place via the triplet state of the ligand. In halogenated and nonhalogenated terbium chelates the ratio of the probability of energy transfer Pt estimated from the quantity IRE⁄Iphτph to the overlap integral S between the phosphorescence spectrum and the terbium absorption spectrum is found to be roughly constant. These results lead us to the conclusion that intramolecular energy transfer is governed by the resonance mechanism due to exchange interaction.
Cyclic Diacylcarbene Generated from Iodonium Ylides and Diazodiketones
Authors: Hayasi Yosio , Okada Taiiti , Kawanisi Mituyosi
Published: July 2006

The preparative method of iodonium ylides, Ph–\overset⊕I–\overset\ominusC(COR)(COR′), is improved by condensation of active methylene compounds, H2C(COR)(COR′), with iodosobenzene in the presence of acetic anhydride. Thermal and Cu-catalyzed decomposition of iodonium ylides can be differentiated and both are explained in terms of diacylcarbene intermediate with different multiplicity. For the sake of comparison diazodimedone and related compounds are also decomposed by Cu-catalysis as well as by photochemical reaction. Carbene is also found to be a highly probable intermediate. Throughout these investigations the spin multiplicity of the carbene is discussed on the basis of product distributions. Notably in the presence of homogeneous Cu-catalyst in ethanol, diazodimedone gives an insertion product to O–H bond, 2-ethoxy-3-hydroxy-5,5-dimethyl-2-cyclohexenone (XVII), whereas the iodonium ylides do not give such a compound. The formation of XVII is explained by assuming a ketocarbene-Cu-chelate complex.
The Synthesis of Poly-l-arginine
Authors: Noguchi Junzo , Fujiwara Yukihiko
Published: July 2006

N ω-Tosyl-l-arginine-Na-carboxylic acid anhydride hydrochloride was obtained as a crystal by the reaction of Na-carbobenzyloxy-Nω-tosyl-l-arginine and thionyl chloride. After treatment with silver oxide to remove the hydrochloride, Nω-tosyl-l-arginine-Nω-carboxylic acid anhydride (NCA) was prepared; it was then polymerized to poly-Na-tosyl-l-arginine(M\fallingdotseq16200, n\fallingdotseq52), which was subsequently converted into poly-l-arginine hydrochloride by treating it with hydrogen fluoride and by passing it through a column of the hydrochloride form of the IRA-400 resin.
Lactone Carboxylic Acids. VII. Reaction of Lactone Pyrazolines with Acetic Anhydride. A Preparation of Lignans Skeleton by Thermal Decomposition of Pyrazoline
Authors: Torii Sigeru , Furuta Takuya
Published: July 2006

Cycloaddition of diazomethanes to aconic acids (4 and 14) gave 1-pyrazolines (5, 7 and 15). Thermal decomposition of 7 afforded γ-phenyl-α-benzylaconic acid 8 having a lignans skeleton. By the action of phosphoric acid 5 was converted into 2-pyrazoline 12. The chemical nature of pyrazolines (5 and 12) is discriminated by treatment with acetic anhydride in the presence of p-toluenesulfonic acid. Thus, 1-pyrazoline 5 gave the corresponding derivatives (10, 11 and 13), and 12 gave 13. The thermochemical stability of the pyrazolines (15 and 16) were also studied. A possible mechanism of the formation of 10 and 13 is described.
The Reactions of Sulfur Ylides with Cyclic Carboxyl Compounds and Isocyanates
Authors: Mukaiyama Teruaki , Higo Moriaki , Takei Hisashi
Published: July 2006

It was found that the reactions of dimethyloxosulfoniummethylide (II) with cyclic carboxyl compounds (I), such as lactones, carboxylic anhydrides and imides, gave the corresponding stable oxosulfonium ylides (III). In addition, the reaction of phenyl isocyanate dimer (IX) and dimethylsulfoniummethylide (X) afforded a 1:1 adduct (XI), which, on heating, decomposed to give a ring expansion product (XIV). Hydantoin derivatives (XVII) were also produced by treating dimethylsulfonium-α-methylacylmethylide (XVI) with two moles of isocyanates in dimethyl sulfoxide. On the other hand, when the same reactions were carried out in benzene, XVI reacted with an equimolar amount of isocyanates to give acrylamide derivatives (XVIII) in high yields by the rearrangement of the intermediate sulfoniummethylide (XX).
The Behavior of Indium(III) Complexes in Several Liquid-Liquid Distribution System. I. A Solvent Extraction Study of Indium(III) Complexes in Aqueous Perchlorate Media Containing Several Anionic Ligands
Authors: Hasegawa Yuko
Published: July 2006

The stabilities of the indium(III) complexes in 4 m sodium perchlorate solutions with eight univalent anionic ligands have been studied at 25°C by using a TTA-chelate extraction method and a TBP adduct extraction method. The following conclusions have been reached. The stabilities of the indium(III) halide complexes are larger in this order; Cl−>Br−>I−; on the other hand, those of indium(III) complexes with the halate anions increase in the order: ClO3−<BrO3−<IO3−. The former forms more stable complexes than the latter. Thiocyanate ions form the most stable indium(III) complexes (the first to the fifth complexes), while nitrate ions form the least stable one (only the first complex). The values obtained by the TTA method are almost identical with those obtained by the TBP method. It was also concluded that although the TTA method could be applied to all the systems studied, it is more suitable for the examination of the lower complexes; the TBP method, on the other hand, could be used only for the systems in which an extractable third complex is formed, but it could give more accurate constants for the higher complexes. Thus, only a combination of these two methods can give all the equilibria in a system where many complexes are formed.
Photoemission from Organic Crystal in Vacuum Ultraviolet Region. IV
Authors: Kochi Masakatsu , Harada Yoshiya , Hirooka Tomohiko , Inokuchi Hiroo
Published: July 2006

The quantum yield and the energy distribution of photoelectrons were measured for organic crystals in the vacuum ultraviolet region. A model was presented for the photoemission from organic crystals with a narrow valence band, and a semiempirical power law was derived for the yield near the threshold. The ionization potentials found from the spectral distribution of the quantum yield using this model were as follows: anthracene–5.68 eV, naphthacene—5.43, pentacene—5.04, perylene—5.33, indanthrone—5.17, and tetrathionaphthacene—4.42. The effect of electrons which escape after one inelastic scattering was observed. It was shown how the contribution of once-scattered electrons can be separated in the energy distribution. The threshold for “pair production” was estimated to be nearly equal to the band gap for perylene and a little higher than the band gap for quaterrylene. The fine structures observed both in the yield spectra and in the energy distribution can be accounted for by assuming the existence of additional valence bands.
Mercury-Photosensitized Reaction of Acetylene
Authors: Shida Shoji , Tsukada Masao
Published: July 2006

The mercury-photosensitized reaction of acetylene has been studied with equimolar mixtures of C2H2 and C2D2 under various conditions of pressure, temperature, and additives. It is shown that the distribution of isotopically substituted benzenes can be explained by a modified excited state mechanism equally as well as, or more favourably than by the free radical mechanism. The results on deuterium-acetylene mixtures photosensitized by Hg(3P1), however, suggest that benzene is also formed by the reaction of hydrogen atoms and acetylene molecules. The rates of benzene formation and of the polymer formation increased gradually with pressure in low pressure region to attain a maximum and then decreased. Argon very strongly inhibited the benzene formation and, to a less extent, the polymer formation. The primary process is explained by assuming the formation of a transient complex of a triplet mercury atom and an acetylene molecule.
The Electronic Spectra of the Anion Radical Salts Derived from Halogen-substituted p-Benzoquinones
Authors: Iida Yôichi
Published: July 2006

The anion-radical salts derived from p-chloranil, 2,5-dibromo-3,6-dichloro-1,4-benzoquinone, and p-bromanil were prepared. The absorption spectra in an acetone solution and the diffuse reflection spectra of the solid salts were examined. These solid salts were then classified into three groups, namely, those showing the spectrum of the anion-radical monomer, those showing a strong charge-transfer band characteristic of the solid salts, and, finally, those showing not only the spectrum of the anion-radical monomer but also an intermolecular charge-transfer band. The mode of intermolecular interaction in these anion-radical salts was discussed according to this classification. Their magnetic behaviour was also speculated upon on the basis of the charge-transfer interaction.
Molecular Structure and the Effect of Large-Amplitude Vibration of Carbon Suboxide as Studied by Gas Electron Diffraction
Authors: Tanimoto Mitsutoshi , Kuchitsu Kozo , Morino Yonezo
Published: July 2006

The molecular structure of carbon suboxide, C3O2, has been studied by the sector-micro-photometer method of gas electron diffraction. The C=O and C=C distances (rg) have been determined to be 1.1632±0.0013 Å and 1.2894±0.0022 Å, respectively, where the uncertainties represent estimated limits of error. The observed mean amplitudes for three nonbonded atom pairs and their shrinkages are found to be much larger than those expected for ordinary molecules, with linear framework. A usual harmonic approximation up to the quadratic terms of displacements cannot account for the observed values in this molecule. This indicates that the πu bending vibration ν7 has a very low frequency (an effective frequency being about 68 cm−1) and that this vibration is essentially a bending motion of the valence angle of the central carbon atom, in agreement with recent spectroscopic studies. The effect of the large-amplitude vibration on mean amplitudes and shrinkages has been studied in detail by using a model, which assumes that atomic motions take curvilinear paths in the ν7 vibration with the valley in the potential surface running along the loci of fixed bond lengths. The potential function for this bending motion has been estimated by a least-squares analysis on the observed structural parameters. The potential function is given by V(Q7)=(23±5)Q74−(100±31)Q72 (cm−1), where the uncertainties representing random standard errors take the upper and lower signs in the same order and Q7= sin α⁄0.145 (amu1⁄2 Å). The potential rises steeply with increasing angle of bending, α=1⁄2[180°∠–(C=C=C)], and appears to have a small hump at α=0. This “quasi-linear” potential function is consistent with the recent experimental estimates by Seip et al. within experimental errors, but the double-minimum nature of the potential is subject to a further critical examination by other experimental methods.
The Precise Coulometric Titration of the Acidic Primary Standard using Amperometric End-point Detection
Authors: Yoshimori Takayoshi , Matsubara Ikuko
Published: July 2006

The sensitive amperometric end-point procedure (Anal. Chem., 23, 1662 (1951)) with an antimony electrode is used in the titrations of acids. The cyclic voltammetric curves of the electrode indicate the possibility of the use of the above method for the titration of acids. The purities of potassium biphthalates (primary standard substances) are determined directly by precise coulometric titration with this end-point location. The standard deviations of the results (99.999%) are 0.007 or 0.008%. The purity of the benzoic acid prepared as the standard material for the calorimeter is also determined by this method. The standard deviation of these results (99.993%) is 0.009%.
Dielectric Relaxation of Esters in Benzene Solutions
Authors: Krishnaji  , Srivastava S C , Nath Dina
Published: July 2006

Dielectric relaxation times and distribution parameters of three esters in benzene solutions have been evaluated using three methods, viz., Cole-Cole arc plot method, Higasi’s single frequency method and the Gopal Krishna method. Three microwave frequencies have been used to determine a′ and a″ apart from the static and optical frequencies for a0  a∞. The distribution parameters obtained from Cole-Cole arc plot and Higasi’s method are in good agreement showing that the sploes a′ and a″ have been determined accurately. In these esters the values of the distribution parameter are high. Since the dipole-dipole interactions are negligible in dilute solutions, the higher values of the distribution parameter suggests the existence of multiple relaxation processes.
The Reactions of Phosphonium Ylides and Oxosulfonium Methylide with Sulfenamide Derivatives
Authors: Mukaiyama Teruaki , Kumamoto Takanobu , Fukuyama Shinichi , Taguchi Takeo
Published: July 2006

It was found that vinyl sulfide derivatives were obtained in good yields by the reactions of carbonyl compounds with α-phenylthioalkylidenetriphenylphosphorane. Phosphorane was prepared by the equimolar reaction of alkylidenetriphenylphosphorane and N-phenylthio-N-methylacetamide. It was established that, differing from the case of alkylidenetriphenylphosphorane, di-methyloxosulfonium methylide reacted with N-phenylthiophthalimide and N-phenylthiosuccin-imide to give N-bis(phenylthio)methylphthalimide and N-bis(phenylthio)methylsuccinimide, re-specitively.
The Friedel-Crafts Reaction of 2,3-Dimethylbenzofuranyl Ketones and the Corresponding Carboxylic Esters
Authors: Kawase Yoshiyuki , Okada Tomoko , Miwa Toshio
Published: July 2006

The acetylation of methyl 2,3-dimethyl-4- and -7-benzofurancarboxylates was carried out by the action of acetyl chloride and aluminum chloride in carbon disulfide at room temperature to afford the 6-acetyl compounds; these compounds were converted to keto-acids by hydrolysis, and then to the known dicarboxylic acid or to the known 6-acetylbenzofuran. The alkylation of acetyl and methoxycarbonyl derivatives of 2,3-dimethylbenzofuran was carried out by the action of n- or iso-propyl bromide and aluminum chloride in carbon disulfide at reflux temperature, both the bromides furnishing the same isopropylated product. The crude products from the 4-acetyl- and 4-methoxycarbonyl-benzofurans could not be purified, but 2,3-dimethyl-6-isopropyl-4-benzofurancarboxylic acid was obtained by the hydrolysis of the product from the latter. In the cases of 5-acetyl- and 5-methoxycarbonyl-benzofurans, the isopropylation occurred at the 7-position and the products were converted to the same carboxylic acids, while the isopropylation occurred at the 4-position in the cases of 6-acetyl- and 6-methoxycarbonylbenzofurans, and diisopropylation occurred in the case of 7-methoxycarbonylbenzofuran.
Chemical Species Produced from Iodine in Stretched PVA Sheets
Authors: Djojosubroto Harjoto , Tanizaki Yoshié , Hoshi Toshihiko
Published: July 2006

A qualitative dichroism analysis has been made on chemical species produced from iodine in stretched sheets of polyvinyl alcohol. The absorption bands at 290 mμ and 360 mμ have been attributed to the bent triiodine ion, and the transition moments of these bands have been found to be parallel to each other. From the optical density ratio (Rd) curve, the presence of a hidden band at about 420 mμ has been pointed out, and the band has been assigned to the absorption by the linear triiodide ion. Three different chemical species are absorbed in the visible region. By comparing the Rd values, the numbers of iodine atoms in the respective species have been estimated.