bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Primary Photochemical Process of 4-Nitropyridine N-Oxide
Authors: Hata Norisuke , Okutsu Eiichi , Tanaka Ikuzo 
Published: July 2006

Abstract
In order to clarify the primary photochemical process of 4-nitropyridine N-oxide in solution, investigations by means of a steady-light irradiation and a flash spectroscopic method were carried out. 4-Nitropyridine N-oxide changes photochemically to 4-hydroxypyridine N-oxide nitrate (Process I) or 4-hydroxylaminopyridine N-oxide (Process II), depending on the reaction conditions. In either case, Process I and Process II, the photochemical reaction was found to proceed through the common intermediate species A. We concluded from the experimental results that Process I involves a bimolecular interaction between the intermediate A and the unexcited 4-nitropyridine N-oxide molecule, while Process II involves a hydrogen-abstracting reaction from a solvent molecule.
Ionization and Dissociation of Formic Acid, Acetic Acid, Propanoic Acid, and Butanoic Acid under Electron Impact
Authors: Ono Yoko , Makita Tutomu , Kodera Kumasaburo 
Published: July 2006

Abstract
The mass spectra of DCOOD, DCOOH, CD3COOD, CD3COOH, CH3COOD, C2H5COOD, and C3H7COOD are compared with spectra of the H-containing compounds. Besides, the 18O-labeled acetic acid is measured. The labeling helps to determine the origin of a number of fragment ions. It is found that the two fragment ions C3H5O2+ and C4H7O2+ are produced by the removal of the hydrogen atom from the alkyl group and have the structures of C2H4CO2H+ and C3H6CO2H+ respectively. Neither CH2CO2H+ nor CH3CO2+ is produced. The rerrangement ion CH3O+ is found to have the structure of CH2OH+, one of whose hydrogen atoms comes from the carboxyl group. The origins of the hydrogen atom and the oxygen atom in the other rearrangement ions are also determined. The mechanisms for the fragmentation of the molecular ions are discussed.
The Peptide Synthesis. II. Use of the Phenol Resin for the Peptide Synthesis
Authors: Inukai Noriyoshi , Nakano Kohzi , Murakami Masuo 
Published: July 2006

Abstract
The phenol resin is useful as support of the solid phase peptide synthesis. Its use is particularly advantageous for the synthesis of the N-protected peptide fragments, and those which have the intramolecular disulfide bond, such as oxytocin. In the latter case, the application of S-ethylmercapto group as the protector of thiol group of cysteine residue was combined successfully. Oxytocin and physalaemin derivatives were thus synthesized.
Solvolysis of cis and trans 2-Cyclohexylcyclohexyl, 2-Phenylcyclohexyl and 2-p-Anisylcyclohexyl p-Toluenesulfonate
Authors: Murahashi Shun-Ichi , Moritani Ichiro 
Published: July 2006

Abstract
trans-2-p-Phenylcyclohexyl p-toluenesulfonate acetolyzes (75°C), at one-eighth of the rate of cyclohexyl p-toluenesulfonate, and one-sixteenth times smaller than that of the cis isomer. trans-2-p-Anisylcyclohexyl p-toluenesulfonate acetolyzes (75°C) much the same as cyclohexyl p-toluenesulfonate, and one-third times smaller than that of the cis isomer. Thus, the slow rate of the trans isomers cannot be interpreted in term of significant phenyl and p-anisylparticipation. This may be due to high cost in energy required to place the aryl group in the axial position where it would be in a favorable position to participate. However, it is noteworthy that the acetolysis of trans-2-p-anisylcyclohexyl p-toluenesulfonate gave trans-2-p-anisylcyclohexyl acetate in 70% yield, which had retention of configuration. The mechanism of this reaction is discussed. The greater reactivities of cis isomers are interpreted in terms of E2 type elimination involving nucleophilic participation by the solvent as well as 2-alkylcyclohexyl p-toluenesulfonate.
Studies of Peptide Antibiotics. XIII. Synthesis of Retrogramicidin S
Authors: Waki Michinori , Izumiya Nobuo 
Published: July 2006

Abstract
In order to investigate a contribution for an antibacterial activity of a direction of the peptide bonds in gramicidin S molecule, retrogramicidin S with the reverse peptide sequence was prepared through a cyclization reaction of linear decapeptide active ester in pyridine. The cyclization of linear pentapeptide active ester yielded a mixture of retrocyclosemigramicidin S and retrogramicidin S. Retrogramicidin S thus obtained exhibited a weak activity against Bacillus subtilis and Staphylococcus aureus, whereas retrocyclosemigramicidin S showed no activity against any of microorganisms tested.
Proton Magnetic Resonance Studies of 2,2′-Anhydro-2-C-hydroxymethyl-1,3 : 4,6-di-O-isopropylidene-l-sorbitol
Authors: Maeda Takashi , Tori Kazuo , Ohtsuru Masako , Tokuyama Kanji 
Published: July 2006

Abstract
The PMR spectra of 2,2′-anhydro-2-C-hydroxymethyl-l,3 : 4,6-di-O-isopropylidene-l-sorbitol were examined in several solvents to confirm its structure. The conformation of this molecule is also discussed.
The Reactions of Esters of Amidosulfurous Acid
Authors: Takei Hisashi , Shimizu Hideo , Higo Moriaki , Mukaiyama Teruaki 
Published: July 2006

Abstract
It was found that benzhydryl dimethylamidosulfite, obtained from N,N,N′,N′-tetramethylsulfurous diamide-phenyl isocyanate adduct and benzhydrol, decomposed to give benzhydryldimethylamine and sulfur dioxide. Similarly, triphenylmethyl and 1,3-diphenylallyl dimethylamidosulfite gave corresponding tertiary amines when these esters were refluxed in benzene. On the other hand, benzoin dimethylamidosulfite gave benzil, the oxidized product of benzoin. When β-anilinoethyl and β-N-methylaminoethyl dimethylamidosulfite were heated at 120–130°C for 10 min, cyclic esters of amidosulfurous acid, 3-phenyl- and 3-methyl-1,2,3-oxathiazolidine-2-oxide, were obtained along with evolution of dimethylamine. Further, the thermal decomposition of the cyclic compounds was studied.
Constituents of Fruit Oil from Japanese Pepper
Authors: Sakai Tsutomu , Yoshihara Kazuo , Hirose Yoshio 
Published: July 2006

Abstract
The steam-volatile constituents from ripe fruits of Japanese pepper have been studied using column and gas chromatographic separations, followed by characterization on the basis of infrared, nuclear magnetic resonance, and mass spectrometry. The capillary gas chromatography of the volatile oil from ripe fruits of Japanese pepper revealed the presence of approximately 130 components. Among the components identified were the following: 19 hydrocarbons (α-pinene, camphene, β-pinene, sabinene, myrcene, α-phellandrene, limonene, β-phellandrene, p-cymene, terpinolene, α-copaene, β-caryophyllene, humulene, γ2-cadinene, α-muurolene, δ-cadinene, γ-cadinene calamenene, and α-calacorene), 15 alcohols (linalool, isopulegol, trans- and cis-2,8-p-menthadien-1-o1, terpinen-4-o1, limonen-4-o1, α-terpineol, 1(7), 8-p-menthadien-trans-2-o1, citronellol, trans- and cis-carveol, geraniol, cuminalcohol, β-caryophyllene alcohol, and nerolidol), 9 aldehydes and ketones (citronellal, dihydrocarvone, cryptone, carvone, piperitone, phellandral, cuminaldehyde, perillaldehyde, and piperitenone), 7 esters (isobutyl isovarelate, isobutyl caproate, linalyl acetate, citronellyl acetate, terpinyl acetate, geranyl acetate, and methyl cinnamate), and 6 oxides (1,8-cineol, β-terpinen-3,4-oxide, trans-and cis-limonen-1,2-oxide, terpinolen-4,8-oxide, and methyl chavicol).
Infrared Spectra of the Addition Compounds of Trimethylamine Oxide with Zinc, Cadmium and Mercuric Halides in the Range 1500–250 cm−1
Authors: Kimura Masao , Kuroda Yoko , Shibuya Ikutoshi 
Published: July 2006

Abstract
Infrared spectra were taken in the region 4000–250 cm−1 for trimethylamine oxide complexes of the type ZnX2L2 and Cd(or Hg)X2L(L=(CH3)3NO and X=Cl, Br or I). Two new bands at about 550 and 400 cm−1 were observed for all complexes. The zinc complexes gave rise to more bands at about 955 and 270 cm−1. Except for these bands, no appreciable change was observed in the vibrational frequencies of trimethylamine oxide upon coordination. These results suggest that the complexes form a tetrahedral arrangement about a metal atom with weak coordinate bonds, and that the crystals of the zinc complexes consist of monomers and those of the cadmium and the mercury complexes of halogen bridged dimeric molecules [MX2L]2.
Syntheses and Properties of Some Dithio-β-diketonato Complexes
Authors: Ouchi Akira , Nakatani Mitsuhisa , Takahashi Yoshiaki 
Published: July 2006

Abstract
Some compounds of type M(Lss)2, where M is Ni(II) or Co(II) and HLss is some dithio derivative of β-diketones (benzoylacetone, trifluoroacetylacetone, trifiuorobenzoylacetone or dibenzoylmethane), were obtained by passing hydrogen chloride and hydrogen sulfide into ethanol solutions containing β-diketone and metal chloride. Such compounds seem to be isostructural to the bis (dithioacetylacetonato) complexes and are stable. They are all deeply colored and their solutions show a characteristic absorption in the visible region, 16700 cm−1 for bis (dithiobenzoylacetonato)nickel(II) and 15200 cm−1 for bis(dithiodibenzoylmethanato)nickel(II). On the other hand, infrared spectra of these complexes show ν(C=S) bands at 1220–1240, 1170–1180 and 840 cm−1. M(Lss)2Cl4 type complexes (where M=Fe(II) or Co(II) and HLss=dithiobenzoylacetone) were also obtained and they seem to be isostructural to Fe(C5H7S2)2Cl4. Their magnetic susceptibilities and electronic and infrared spectra are shown and discussed.
Polarographic Behavior of Tris(2,2′-bipyridine)manganese(II) in Acetonitrile Solutions
Authors: Sato Yuichi , Tanaka Nobuyuki 
Published: July 2006

Abstract
Polarographic behavior of tris(2,2′-bipyridine)manganese(II) perchlorate at the dropping mercury electrode in acetonitrile solutions has been investigated by the measurement of d.c., a.c. and Kalousek polarograms. The manganese(II) complex gave a five-step reduction wave and a one-step oxidation wave at the dropping mercury electrode when tetraethylammonium perchlorate was used as supporting electrolyte. In the presence of a large concentration of free 2,2′-bipyridine, the limiting currents of the first three steps of the reduction of the manganese(II) complex are all diffusion-controlled and of a one-electron reduction process. The electrode processes for these steps have been concluded to be the reductions to [Mn(bipy)3]+, [Mn(bipy)3] and [Mn(bipy)3]−, respectively.
The Rearrangement of Isoflavanone Oximes with Lithium Aluminum Hydride
Authors: Inoue Naoto , Yamaguchi Shozo , Ito Shoei , Suzuki Ikuko 
Published: July 2006

Abstract
The reaction of isoflavanone oxime (III), 7-methoxyisoflavanone oxime (IV), and 4′,7-dimethoxyisoflavanone oxime (V) with lithium aluminum hydride in ether for 20 hr under refluxing gave 3-phenyl-2,3,4,5-tetrahydro-1,5-benzoxazepine derivatives (XVII, XVIII and XIX) but not the expected 4-aminoisoflavans. When a similar reaction was carried out using flavanone oxime and 7-methoxyflavanone oxime, only 4-aminoflavans were obtained, and the rearrangement reaction observed in isoflavanone oximes did not occur. Therefore, it may be considered that, in the reaction of chromanone oximes and lithium aluminum hydride, the position (C2 or C3) and the size of the substituent exerts a remarkable influence on the rearrangement reaction, while the methoxyl group at the 7-position (para position to the oximino group) has little effect.
Synthesis and Properties of Nitrosoazulenes
Authors: Nozoe Tetsuo , Yang Paw Wang , Ogawa Hiroshi , Toda Takashi 
Published: July 2006

Abstract
Ethyl 2-amino-3-nitrosoazulene-1-carboxylate (II) was synthesized from ethyl 2-aminoazulene-1-carboxylate by treatment with isoamyl nitrite. The structure of the amino-nitrosoazulene was proved by the reductive acetylation of the azulene to give ethyl 2,3-diacetylaminoazulene-1-carboxylate. This nitrosation method was then applied to several azulenes possessing different substituents; it yielded some stable nitrosoazulene derivatives. The spectral properties of the nitrosoazulenes will be discussed. The condensation reactions of II with aromatic amines failed to give azo-dyes, but with diethyl malonate and malononitril they gave the corresponding pyrazinoazulene derivatives.
Ring-opening Polymerization of Norbornene and Its Derivatives by MoCl5, WCl6 and ReCl5 Catalysts
Authors: Oshika Takao , Tabuchi Hiroyoshi 
Published: July 2006

Abstract
Norbornene and such of its derivatives as exo-5,6-trimethylene norbornene (exo-TMN) and endo-dicyclopentadiene (endo-DCPT) have been polymerized via ring cleavage to high-molecularweight polymers, soluble in aromatics, by the use of MoCl5, WCl6, and ReCl5 catalysts in a carbon tetrachloride solvent. The ring-opening polymers obtained by MoCl5 have a trans-structure almost exclusively, on the other hand the polymers obtained by ReCl5 are rich in cis structures and those obtained by WCl6 are mixtures of the two. The reactivities of the monomers on those catalysts have been found to have the order of decreasing reactivity: exo-TMN&gt;NE&gt;endo-DCPD. In the ring-opening polymerization of norbornene by MoCl5, carbon disulfide and carbon tetrachloride have been found to be effective solvents. The yield increases with the rise in temperature and also upon the addition of a catalytic amount of tertiary amines in the midst of the polymerization procedure, while the structures of the polymers obtained do not change. The Co-catalyst H2O is not necessary. Chlorine atoms are found in the polymers. Those results suggest that the ring-opening polymerization of norbornene over MoCl5 occurs through a specific coordinated mechanism.
The Preparation and Cycloaddition Reactions of Pentafluoro-1,3-pentadienes
Authors: Muramatsu Hiroshige , Inukai Kan , Ueda Teruo 
Published: July 2006

Abstract
3,4,5,5,5-Pentafluoro-1,3-pentadienes were prepared from 1 : 1 adducts of perfluoropropylene and alcohols by dehydration followed by dehydrofluorination. When 2-methyl-3,4,5,5,5-pentafluoro-1,3-pentadiene was heated at 130–220°C, an intramolecular cyclization occurred to give 1-methyl-2,3-difluoro-3-trifluoromethylcyclobutene in 73–87% yields. α-Trifluoromethyl-β-acetylacrylic acid and 1-trifluoromethyl-2-fluoro-3-methylenecyclobutene were synthesized from the cyclobutene by oxidation and dehydrofluorination, respectively. Several polyfluorocyclobutanes with a perfluoropropenyl group were prepared by the cross-cycloaddition of the pentafluoro-1,3-pentadienes with the fluoroolefins such as 1,1-difluoro-2,2-dichloroethylene, trifluorochloroethylene, and perfluoropropylene.
Oxazolidone Derivatives of Hydroxyamino Acids. V. New Synthesis of threo- and erythro-β-Hydroxy-Dl-aspartic Acids
Authors: Inui Toshishige , Ohta Yoshimoto , Ujike Toshiaki , Katsura Hakuji , Kaneko Takeo 
Published: July 2006

Abstract
threo- and erythro-β-Hydroxy-Dl-aspartic acids (VI and X) were synthesized by oxidation and subsequent hydrolysis of Dl-trans- and Dl-cis-5-furyl-2-oxo-oxazolidine-4-carboxylic acids (IV and VIII) derived from threo- and erythro-β-furyl-Dl-serines (III and VII) respectively.
Selective Chemical Cleavage of Threonine Peptides
Authors: Kaneko Takeo , Kusumoto Shoichi , Inui Toshishige , Shiba Tetsuo 
Published: July 2006

Abstract
Threonine peptide was converted to an oxazolidone derivative via an O-chlorocarbonyl derivative by treatment with phosgene and dimethylaniline followed by refluxing in xylene, wherever the threonine residue was located in peptide chain, that is, either at amino or carboxyl terminal, or in the middle of the chain. When the oxazolidone peptide was treated with alkali at room temperature, the peptide bond of the original threonine residue of which the amino group participated was selectively cleaved giving a mixture of the carboxylic acid derived from the N-terminal amino acid or peptide, and 5-methyl-2-oxo-oxazolidine-4-carbonyl derivative, whereas other peptide bonds remained unchanged in this reaction. Several threonine peptides were synthesized and were subjected to the cleavage reaction. In all cases the expected cleavage occurred in a satisfactory yield.
The Effect of the ω-Cyano Group on the Reactivity of Secondary Bromides in the Formolysis Reaction and on the Reactivity of Primary Bromides in the Reaction with Silver Nitrate
Authors: Strilko Peter S , Morita Hiroyuki , Oae Shigeru 
Published: July 2006

Abstract
Several ω-cyano-2-bromoalkanes have been synthesized and their formolysis rates were determined. The reactivity of these compounds was found to decrease with a decrease in chain length and have a parallerism with a chemical shift (&gt;CH–, –CH3) of NMR spectra. A similar sequence was observed in the reactivity of ω-cyano-1-bromoalkanes in the reaction with silver nitrate.
The Reaction of Benzylic Alcohols with Dimethyl Sulfoxide-Polyphosphoric Acid
Authors: Sato Takeo , Takatsu Akihiko , Saito Yoshitaka , Tohyama Takafumi , Hata Kazuo 
Published: July 2006

Abstract
The reaction of dimethyl sulfoxide-polyphosphoric acid mixture with benzylic alcohols has been shown to afford a complex mixture of the products; this is in contrast to the case of aliphatic alcohols, which yield the corresponding acetal as the major product. By carrying out reactions using several benzylic alcohols and a series of benzyl alcohols, it was found that, in addition to the acetal formation reaction, dehydration and oxidation reactions, as well as a methyl thioether-formation reaction, were occurring. Possible pathways for the formation of these products are presented.
Kinetic Studies of the Catalytic Ortho-Parahydrogen Conversion and Hydrogen-Deuterium Equilibration on γ-Alumina
Authors: Ohno Seigo , Yasumori Iwao 
Published: July 2006

Abstract
Kinetic studies of the catalytic ortho-parahydrogen conversion and hydrogen-deuterium equilibration on highly purified γ-alumina were conducted in the range of temperature from 77 to 221°K and in the range of pressure from 10 to 120 mmHg. The rate equation obtained can be well explained by a mechanism which involves the reaction between an adsorbed atom and a molecule. The true activation energy, E, and the heat of adsorption of the reactive molecule, Q, were estimated as E=0.51–0.80 and Q=0.51–0.72 kcal/mol for the conversion (77–95°K), and E=4.6 and Q=1.9 kcal/mol for the equilibration (145–221°K). The conversion at temperatures below 90°K was found to proceed mostly via the magnetic mechanism. A thermal desorption study of adsorbed ethylene showed that there are three types of adsorption on γ-alumina with different activation energies of desorption, and that these species occupy a total of only a few hundredths of the surface. It was concluded that the most strongly-adsorbed ethylene blocks the reactions via the chemical mechanism, while the most weakly-adsorbed one retards the conversion via the magnetic mechanism. The nature of active sites for the reactions was discussed by taking the results of the ESR measurement into consideration.
SCFMO Parameters for Heteroatoms donating Lone Pairs
Authors: Nishimoto Kichisuke , Forster Leslie S 
Published: July 2006

Abstract
The interrelationships between the semi-empirical parameters involved in SCFMO calculations have been considered. The calculated transition energies for molecules containing an atom that donates two electrons to the π-system are mainly dependent upon the first valence state ionization energy of the heteroatom, and the nearest-neighbor two center repulsion integrals.
Changes in Catalytic Activity and Surface Properties of Nickel Oxide with Gamma-Irradiation
Authors: Yamashina Toshiro , Nagamatsuya Takaaki , Sano Masakatsu 
Published: July 2006

Abstract
The nature of the active sites of nickel oxide has been studied by changing surface properties by means of γ-irradiation technique. Using powdered nickel oxide catalyst, catalytic activities, surface excess oxygen contents, electrical conductivity changes during thermal desorption of gases, and reactivities of the sample with CO2, CO and H2 were compared as a function of γ-ray dose of preirradiation. It has been found that the catalytic activity, the excess oxygen content and the conductivity change with the increase in the irradiation dose, and the change is remarkable when a total dose is greater than 1×108R. The catalytic activity for the decomposition of H2O2 was observed to increase, while that for the decomposition of i-C3H7OH vapor was observed to decrease with the irradiation dose. Measurements on the desorption of excess oxygen and the adsorption of CO2 simultaneously with electrical conductivity have indicated that the adsorbed state of surface oxygen may be changed into a strong form by the irradiation, as O−(ad) \ightsquigarrow O2−(ad). Discussions have been made on the correlation between the catalytic sites and surface properties of the irradiated nickel oxide.
Retardation of Polarographic Oxidation of Ethylenediaminetetraacetatocobaltate(II) by Mercury(I) Iodide Film Formation
Authors: Tanaka Nobuyuki , Yamamoto Setsuko , Sato Yuichi 
Published: July 2006

Abstract
The electrode process of ethylenediaminetetraacetatocobaltate(II) (CoIIY2−) at the dropping mercury electrode has been studied in the presence of iodide ions. It was found that polarographic anodic waves of CoIIY2− were affected by the film of mercury(I) iodide which was formed electrolytically at the electrode surface. The measurement of current-time curves during the life of a mercury drop and the coulometric studies revealed that the electro-oxidation of CoIIY2− was completely inhibited by the formation of monomolecular layer of mercury(I) iodide on the mercury surface.
Silent Discharge Reactions in Aqueous Solutions. VIII. Effects of Discharge Gap Distance and Discharge Current on the Yield of Decomposition Products Formed from Water in Argon Atmosphere
Authors: Yokohata Akira , Harakon Katsuyuki , Tsuda Satoru 
Published: July 2006

Abstract
In order to elucidate the effects of discharge gap distance and discharge current on SGH2O2, SGOH and SGH, the study of this series was further made by using a new discharge apparatus. Both of acidic aqueous solutions of ferrous sulfate and ferrous sulfate-cupric sulfate have been selected as the reaction systems suitable for this purpose. Experiments were made in the range from 3 mm to 9 mm of discharge gap distance and from 0.2 mA to 0.5 mA of discharge current. Each SG value of H2O2, OH and H varied with gap distance (5→9 mm) and current (0.2→0.5 mA) as follows; in the former, 1.0→1.2, 1.8→0.9 and 1.1→0.9: in the latter, 1.4→1.2, 0.6→0.9, 0.8→0.9. Based on the value of Y(H2O2)/Y(H+OH), it was concluded that (1) the silent discharge reactions under a longer gap distance correspond to the radiolysis having a value of higher LET, that (2) although those under a lower current do also to a higher one, the effect of discharge current on the value of apparent LET is relatively small.
Studies on the Electronic Spectra of the Semiquinones of Anthracene and Its Related Heterocycles. I
Authors: Masuhara Hiroshi , Okuda Michio , Koizumi Masao 
Published: July 2006

Abstract
Electronic absorption spectra of two types of half reduced acridine, i. e., C-radical (unpaired electron on 9-C-atom) and N-radical (unpaired electron on N-atom), of half-reduced anthracene and of xanthene deprived of one hydrogen atom, are measured in several rigid solvents at 77°K. It has been established that these radicals can be produced conveniently by irradiating the rigid solutions of the reduced forms, by a medium high pressure mercury lamp. It has been found that the absorption spectra of these radical species are generally classified into three groups, a) ∼250 nm (4.9 eV), b) ∼350 nm (3.5 eV) and c) visible (2.3–2.8 eV). Peculiar features for each radical species are; i) anthracene radical has no visible absorption, ii) acridine N-radical has no absorption at ∼250 nm, and iii) acridine C-radical has a prominent sharp peak at 281 nm. Flash photolytic and ESR studies have also been performed on the radical species produced upon irradiation of dihydroanthracene and xanthene; the results obtained have substantiated the assignment of the intermediates observed in rigid solvents.