bluuebunny/crossref_metadata_2025 huggingface dataset:
Azirines. III. The Preparation of Azirine Derivatives by the Base-Catalyzed Rearrangement of Quaternary Hydrazones
Authors: Sato Shimao
Published: July 2006

An attempt to prepare azirines by the base-catalyzed rearrangement of some quaternary hydrazones gave the corresponding azirine derivatives. Namely, 2-phenyl-3-methylazirine was obtained by the treatment of propiophenone dimethylhydrazone methiodide with potassium t-butoxide, but treatment with sodium isopropoxide gave 2,5-diphenyl-3,6-dimethylpyrazine or 2-phenyl-2-isopropoxy-3-methylaziridine, depending on the reaction conditions. 2-Phenyl-3,3-pentamethyleneazirine was obtained in a good yield by the treatment of cyclohexyl phenyl ketone dimethylhydrazone methiodide with sodium isopropoxide.
Investigation of Copper(II) Chelate with Chromotropic Acid
Authors: Wake Ryousuke , Miyata Haruo , Tôei Kyoji
Published: July 2006

Copper(II)-chelate with chromotropic acid was investigated by potentiometric titration. The measurement have been carried out at 25.0±0.1°C and μ=0.10 (with KNO3). The acid dissociation constant of chromotropic acid, the formation constant of the 1 : 1 chelate (the molar ratio of ligand to copper(II) ion) and th hydrolysis constant of this chelate were determined.
Reaction of Butadiene with Ethylene. IV. Synthesis of 1,4-Hexadiene by a Cobaltous Chloride-Ditertiary Phosphine Complex and an Organoaluminum Compound Catalyst
Authors: Iwamoto Masao , Yuguchi Sadao
Published: July 2006

A new catalyst consisting of a cobaltous chloride-ditertiary phosphine complex and an organoaluminum compound was found to be effective for the selective preparation of 1, 4-hexadiene by the reaction of butadiene with ethylene. The effects of the reaction variables on the activity and on the selectivity in 1, 4-hexadiene formation were studied. It is considered that a coordination of the ditertiary phosphine on the catalytically activated intermediate is essential for the selective catalysis. A reaction mechanism is proposed which involves an activated hydrido-cobalt complex as intermediate.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. IV. The Anion Radicals of Some Substituted Methyl Benzoates
Authors: Hirayama Masatoshi , Isobe Taro
Published: July 2006

ESR spectra are observed for the anion radicals of methyl p-, m- and o-nitrobenzoates, methyl ester of p-phthalaldehydic acid, and methyl and ethyl p-cyanobenzoates. Both the electrolytic and alkali-metal reduction methods are used for the radical generation. The spin densities calculated by McLachlan’s procedure only with the adjustment of the resonance-integral parameter for the ester group-ring bond are in good agreement with those obtained experimentally for most of the substituted positions in these radicals. The result for the methyl o-nitrobenzoate anion suggests that the ester group is twisted considerably by the large steric hindrance between the ester and nitro groups. The ring-proton splittings of three p-substituted methyl benzoate anions show that the known order of electron-withdrawing effects of the substituents, NO2>CHO>COCH3>COOCH3>CN, holds also for these anions. And it is suggested that the electron-withdrawing power of a XM+ group produced on the alkali-metal reduction increases in the order of free NO2, NO2Cs+,NO2K+,NO2Na+ and NO2Li+, and that the groups CHONa+ and CHOK+ are more electron-withdrawing than a free CHO group. The ring-proton splittings obtained from the VB-superposition calculations for all the anions except for the o-derivative are in satisfactory agreement with those from the MO calculations. Structural models of ion complexes are proposed for the p- and m-nitro derivatives and methyl ester of p-phthalaldehydic acid with the assistance of MO calculations.
Deuteron Magnetic Resonance of NiSiF6·6D2O and NiSnCl6·6D2O
Authors: Chiba Takehiko , Soda Gen
Published: July 2006

Deuteron magnetic resonance study was made on single crystals of NiSiF6·6D2O and NiSnCl6·6D2O. Deuteron quadrupole coupling tensors were determined at various temperatures. In NiSiF6·6D2O, the quadrupole coupling at −116°C is that of stationary D2O, at 23°C and at 70°C that of D2O under rapid 180°-flip motion and at 150°C that of rapid Ni(D2O)62+ reorientation. The eqQ⁄h values at −116°C, 238.3±1.3 kc and 235.7±1.9 kc do not appear to show marked effect of strong coordination. In NiSnCl6·6D2O, the quadrupole coupling corresponding to D2O under 180°-flip motion is observed at −53°C, at 25°C, and at 55°C. Spectra corresponding to a stationary D2O are not observed even at 77 °K. From the orientation of quadrupole tensors probable crystal structures of these compounds are proposed. Line width transitions were observed from which the reorientation rate was derived. The estimated activation energies of the 180°-flip motion of D2O are 7.6 and 4.3 kcal/mol in the fluosilicate and chlorostannate, respectively, and that of Ni(D2O)62+ reorientation in the fluosilicate is 19 kcal/mol. Additional measurements of 19F and 1H resonances indicate the setting in of the SiF62− reorientation at −110°–−120°C in NiSiF6·6H2O, and that of the Ni(H2O)62+ reorientation in the chlorostannate at approximately the same temperature as the fluosilicate.
The Diffusion of Gases at High Pressures. II. The Diffusion of 14CO2 in the 12CO2-Ar System
Authors: Takahashi Shinji
Published: July 2006

The diffusion coefficients of 14CO2 in argon and in binary mixtures of normal carbon dioxide and argon were measured at the temperatures of 25, 50 and 75°C in the 15—250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell using the radioactive tracer technique. The products of the binary diffusion coefficient of 14CO2 in argon and the density increase with an increase in the density. This tendency is not predicted by Enskog-Thorne’s mixed dense gas theory, which requires that the products decrease with an increase in the density. The products of the diffusion coefficient of 14CO2 in the mixtures and the density increase slightly with an increase in the density in the region of lower density at each temperature. However, in the region of higher density they decrease slightly at 25 and 50°C and are nearly constant at 75 °C. The values extrapolated to 1 atm agree fairly well with the experimental findings of Holsen et al. and those predicted by kinetic theory.
Liquidus Curve Measurements in the ZrO2-MgO System with the Solar Furnace
Authors: Noguchi Tetsuo , Mizuno Masao
Published: July 2006

A liquidus curve in the system ZrO2-MgO was investigated by the use of a heliostat type solar furnace. The cooling curves of a composition were obtained by the specular reflection method with a brightness pyrometer. Quenched specimens from the melt were examined with an X-ray technique and a petrographic microscope. Newly found anomalies on the liquidus curve were 7.5, 12.5 and 17.5 mol% MgO compositions. The composition of 12.5 mol% MgO quenched from the melt showed the new cubic-like phase of which optic angle of 2 V equals to −74°C and decomposed easily into monoclinic and tetragonal forms by reheating at 1300°C.
An Experimental Study on the Role of Water Vapor in the Distribution of Fluorine and Chlorine in Volcanic Rocks
Authors: Sugiura Tsutomu
Published: July 2006

Fluorine and chlorine contents of volcanic rocks were examined with respect to the characteristics of the rocks. Fluorine showed rather linear relationships with some chemical components of the rocks and also with stages in the differentiation of magmas. But any universal relationship covering all the rock types was not found. The cause of this fact is expected to be the loss of halogens from rocks resulted from the interaction between rocks and water vapor, which is believed to be ubiquitous in magma and is gradually emanated from it during or after the formation of rocks. So, in order to make clear the role of water vapor in the distribution of halogens in rocks, the author has distilled fluorine and chlorine from rock samples with water vapor at elevated temperatures and studied following relations; (1) the relationship between the amount of distilled halogens and the fluorine and chlorine contents of the rocks, and (2) the relationship between the amount of distilled halogens and the characteristics of the rocks. In distillation of fluorine and chlorine with water vapor, almost all fluorine remained in each rock specimen at low temperatures below 300°C, and at temperatures above 700°C the ratio of the amount of distilled fluorine to the initial amount of fluorine in rocks fluctuated among specimens. However, there was no relation between patterns of the distilled fluorine and the fluorine content of the rocks, and also the characteristics of the rocks. Meanwhile, distillation curve of chlorine showed various patterns without having any relation to chlorine content of the rocks, and indicated that chlorine was retained more in basic rocks than in acidic rocks at higher temperatures, although no relation was observed between the chlorine content of the rocks and the characteristics of the rocks. Generally the ratio of distilled fluorine to initial fluorine in rocks is smaller than the ratio of distilled chlorine to initial chlorine in rocks at low temperatures. The results of the distillation experiments suggest that the distillation process of halogens with water vapor controlls the distribution of halogens in volcanic rocks more than does the chemical and mineralogical nature of the rocks.
Short-Lived Nuclides Formed by (γ, n) Reactions with 20MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Yamadera Akira
Published: July 2006

The most prominent (γ, n) reaction products with half-lives from 10 sec to about 1 min formed by irradiation of some 7 elements with 20 MeV bremsstrahlung have been determined in order to study the applicability of these products to photoactivation analyses. Irradiation was carried out for 1 min with 20 MeV bremsstrahlung radiation with a dose rate of 107 R/min. The reactions investigated are 24Mg(γ, n)23Mg, 76Ge(γ, n)75mGe, 78Se(γ, n)77mSe, 92Mo(γ, n)91mMo, 140Ce(γ, n)139mCe, 142Nd(γ, n)141mNd and 159Tb(γ, n)158mTb. The yields of these reactions have also been obtained through the absolute measurement of resultant activities. The isomeric yield ratios have been discussed on the basis of the nuclear properties of the residual nuclides. The observed ratios generally favor the isomer whose spin is closer to that of the target nucleus. For the elements studied, the lower limits of detection averaged about 1 μg under present experimental conditions.
A New Synthesis of Pyridoxal-5-phosphate
Authors: Iwanami Masaru , Numata Toshiko , Murakami Masuo
Published: July 2006

By the hydrolysis of pyridoxal-5-phosphate Schiff bases, pyridoxal-5-phosphate was prepared in a crystalline form without any further purification. Pyridoxal-5-phosphate Schiff bases were prepared in good yields by the phosphorylation of pyridoxal Scruff bases and were easily purified by alkali-acid reprecipitation. The pyridoxal-5-phosphate thus obtained was demonstrated to be identical with an authentic sample by a study of its UV, IR, and NMR spectra.
Kinetics of the Aquation of Pentammine Amino Acid Cobalt(III) Complexes
Authors: Ogino Kazuko , Murakami Tasuku , Saito Kazuo
Published: July 2006

The rate of aquation of pentamminecobalt(III) complexes of the general formula [Co(NH3)5amH]3+ (amH stands for an amino acid molecule with proton on the nitrogen atom), containing unidentate glycine, β-alanine, sarcosine and betaine, has been measured at 55°C, and ionic strength 0.1 and 1.0 in the acid concentration range up to 0.5 m. The kinetic term is expressed by

Rate=[complex](k_H_2O+k_H^+[H^+])

The kH2O and kH+ values for glycine, β-alanine, sarcosine and betaine complex are respectively as follows (at μ=1.0): kH2O, 0.40×10−6, \lesssim0.2×10−6, 0.25×10−6, and 0.44×10−6 sec−1; kH+, 2.0×10−6, 26×10−6, 1.8×10−5, and 1.0×10−6  m−1 sec−1. The kH+ alues increase with increase in pKa values of the amino acids, but are smaller than those for the aquation of carboxyl-atopentamminecobalt(III) complexes. This difference seems to be due to the electrostatic shielding of the car boxy late group by the protonated amino group.
The Cyclization of Ethyl Acetoacetate and Ketones by Ammonium Acetate
Authors: Sakurai Akio , Midorikawa Hiroshi
Published: July 2006

The reactions of ethyl acetoacetate with cyclic ketones and aromatic methyl ketones by using excessive ammonium acetate gave some heterocyclic compounds, such as 2-hydroxy-4-methyl-5, 6, 7, 8-tetrahydroquinoline (III), 2-hydroxy-4-methyl-6, 7-dihydro-5H-1-pyrindine (IV), and 2-hydroxy-4-methyl-6-alkyl-pyridines (VI). The structures of these compounds were investigated by means of their infrared and NMR spectra.
Studies of the N-Oxides of N,N-Dialkylainino Acids. I. The Syntheses of N,N-Dimethyl Neutral Amino Acids and Corresponding N-Oxides
Authors: Ikutani Yoshikazu
Published: July 2006

The N,N-dimethyl derivatives of neutral amino acids, such as glycine. l-alanine, Dl-alanine, l-valine, Dl-valine, l-leucine, l-phenylalanine, and l-tyrosine, were prepared by the catalytic reductive condensation of the corresponding amino acids with formaldehyde. The N-oxides were satisfactorily synthesized by the oxidation of the N,N-dimethyl derivatives with an aqueous mixture of hydrogen peroxide and acetic acid. The reaction conditions, the analytical data, and some properties of the products are presented.
Stability of Hydrosol of Arsenic Trisulphide in the Light of D. L. V. O. Theory
Authors: Daluja K L , Srivastava S N
Published: July 2006

The stability of negative As2S3 sol of mean particle diameter 90 Å has been studied in presence of different valent cations viz. Na+, Ba2+, UO22+, Al3+ and Th4+ using D. L. V. O. theory. The zeta potential (assumed to be equal to the surface potential) of the sol particles was calculated from the electrophoretic measurements as a function of ionic strength. The knowledge of zeta potential permitted the calculation of repulsive energy VR, and the energy of attraction VA was estimated from physico-chemical data. The stability ratio, W was calculated from interaction profiles which were made from the combination of the two energies. Stability factor, F, was also estimated from the Derjaguin equation, but it was not satisfactory presumably owing to the exclusion of VA. In general, the interaction between As2S3 particles could be interpreted in the light of D. L. V. O. theory. The flocculation powers of cations were in the order of Al3+>Th4+>UO2+>Ba2+>Na+. The anomalous behaviour of thorium is perhaps due to its hydrolysis.
The Wolff Rearrangement. IV. The Silver-salt Catalyzed Decomposition of α-Diazoacetophenones in Benzene Solution
Authors: Takebayashi Matsuji , Ibata Toshikazu
Published: July 2006

The decomposition of α-diazoacetophenone (I) in benzene solution has been studied using a silver benzoate-triethylamine catalyst at 50°C in an atmosphere of nitrogen. The reaction gave 3-benzoyl-4-hydroxy-5-phenylpyrazole (II) and β-phenylpropiophenone (III). In the decomposition of the substituted compounds, such as p-methoxy-, p-methyl- and p-nitro-α-diazoacetophenones, the corresponding substituent products of II and III were also obtained. The formation of II and III is reasonably explained by assuming two kinds of reactions between phenylketene and I.
Photochemischer Zerfall von Benzoylphenylacetyl- und Benzoyl-p-chlorphenylacetyl-peroxyden in Toluol
Authors: Suehiro Tadashi , Hibino Shuji , Saito Tadashi
Published: July 2006

Benzoylphenylacetylperoxyd und Benzoyl-p-chlorphenylacetylperoxyd zerfallen photolytisch in Toluol bei −5–−10°C in die Benzoyloxy und Benzyl bzw. p-Chlorbenzyl Radikale unter Bildung von Kohlendioxyd, Benzoesäure, Benzoesäure-benzyl- bzw. -p-chlorbenzyl-ester, Bibenzyle, Methyldiphenylmethane, Diphenylmethane und Methyldiphenyle. Eine Umlagerungsreaktion vom Peroxyd in den Benzylkohlensaurebenzoesäureanhydrid verläuft nebenbei und dieser Anhydrid liefert durch Einwirkung auf Benzoesaure, Kohlendioxyd, Benzylalkohol und Benzoesäureanhydrid. Die freie Radikale Reaktion und die Umlagerung in den Kohlensäureanhydrid vom Peroxyd finden im Verhältnis ca. 2:1 statt. Aus dem Lösungsmittel, Toluol, entsteht Benzyl Radikale wahrend der Photolyse durch Einwirkung von Benzoyloxy Radikal, dies wurde durch das Vorkommen von Bibenzyl und p-Chlorbibenzyl bei der Photolyse von Benzoyl-p-chlorphenylacetylperoxyd in Toluol nachgewiesen.
Magnesium Ammonium Phosphates, Related Salts and Their Behavior in Compound Fertilizers
Authors: Ando Jumpei , Akiyama Takashi , Morita Matsusaburo
Published: July 2006

Fluorine forms a previously unknown compound MgNH4HFPO4 (MAFP) when monoammonium phosphate made from wet-process phosphoric acid is treated with magnesium hydroxide above about 75°C in the presence of moisture. When treatment is conducted with a large quantity of water, fluorine forms a gelatinous material which resembles MAFP in chemical composition. Wet-process phosphoric acid ammoniated and reacted with magnesium hydroxide above about 75°C gives a very thick slurry, which almost solidifies due to the formation of gelatinous material, while the acid treated in the same way after being defluorinated gives a less viscous slurry in which most of the magnesium is present in the form of MgNH4PO4·H2O (MH). Fluorine shows less effect at lower temperature. When treated below about 60°C, most of the magnesium combines to form MgNH4PO4·6H2O (M6H) and Mg(NH4)2(HPO4)2·4H2O (M4H). M6H and M4H decompose during drying at about 100°C, losing ammonia and water of crystallization to form amorphous materials. The decomposition is promoted by the presence of potassium salts resulting in the formation of water-insoluble potassium. Another previously unknown compound, MgKHFPO4 (MKFP), which is isomorphic with MAFP has also been identified. MKFP is less soluble in water while MAFP decomposes in water to precipitate amorphous material and M6H. Solid solutions of MAFP and MKFP are often present in commercial fertilizers, and provide a small amount of water-insoluble potassium. M4H decomposes rapidly in water to precipitate M6H. M6H and MH are less soluble in pure water but are considerably soluble in water which contains acidic salts, such as monoammonium phosphate.
Phase Transitions and Thermodynamic Properties of Rubidium and Cesium Cyanides
Authors: Sugisaki Masayasu , Matsuo Takasuke , Suga Hiroshi , Seki Syûzô
Published: July 2006

Heat-capacity measurements were performed for rubidium and cesium cyanide crystals between 15 and 300°K. It is found that each crystal has only one anomalous peak in its heat capacity curve, being located at 110.3°K and 193.1°K for rubidium and cesium cyanides, respectively. By the comparison of the present data with those for potassium and sodium cyanides, it was shown that these anomalous heat capacities can be interpreted in terms of the orientational ordering processes of cyanide ions in the crystals. It was suggested that there should exist the residual entropy due to the frozen-in state in their orientational configuration and they were estimated as Rln4 for rubidium cyanide and Rln2 for cesium cyanide.
Intramolecular Interaction between Hydroxyl Group and Carbonyl Moiety in Keto-alcohols
Authors: Oki Michinori , Iwamura Hiizu , Aihara Jun-ichi , Iida Hiroshi
Published: July 2006

The O–H stretching absorption (νO–H) spectra of some keto-alcohols have been examined. The νO–H shift to the lower frequency due to the intramolecular O–H··· bonding can roughly be correlated to the geometry of the hydroxyl group relative to the n-electrons on the carbonyl oxygen. When the bonding is forbidden because of the conformational restriction, a weaker interaction between the hydroxyl group and the π-electrons on the carbonyl group is observable as the lower shift of the νO–H by 10–30 cm−1 as far as the conformation is favorable for the interaction.
Kinetic Studies of Ammonia Oxidation in Shock Waves. IV. Comparison of Induction Periods for the Ignition of NH3-O2-N2 with Those for NH3-O2-Ar Mixtures
Authors: Miyama Hajime
Published: July 2006

Induction periods for ammonia oxidation in the NH3-O2-Ar and NH3-O2-N2 mixtures were measured by monitoring an ultraviolet absorption of ammonia in reflected shock waves. For the NH3-O2-Ar mixtures, induction periods in the temperature range of 1450–2730°K were found to be expressed by

logτ_i[O_2](mol·l^-1μsec)=-(16.24±0.17)+(10080±320)/T

when oxygen content is in the range of 4–10%, and by

long τ_i(μsec)=-(2.55±0.14)+(8810±220)/T

when the oxygen content is less than 1%. Values of induction periods for the 0.5% NH3-0.5%O2-99%N2 and 1% NH3-1%O2-98%N2 mixtures were also measured and compared with those for the NH3-O2 mixtures highly diluted with argon. Both results agreed well by taking into account vibrational relaxation of the reacting system if appropriate values of vibrational relaxation times for N2 dilute in NH3 is assumed. Therefore, possibility of coupling of vibrational relaxation of N2 and oxidation reaction was considered to be small.
The Primary Photochemical Process of 4-Nitropyridine N-Oxide
Authors: Hata Norisuke , Okutsu Eiichi , Tanaka Ikuzo
Published: July 2006

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

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

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

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

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

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

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

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

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

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

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

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

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

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>NE>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

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

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

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

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 (>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

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

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

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

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

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

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

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.
Dilute Solution Properties of Monodisperse Poly(α-methyl styrene). I. Sedimentation Coefficient in Theta Solvent
Authors: Abe Mitsuo , Sakato Kuniaki , Kageyama Takashi , Fukatsu Masaaki , Kurata Michio
Published: July 2006

The sedimentation behavior of anionically polymerized poly (α-methyl styrene) has been studied as a function of molecular weight, concentration and speed of centrifugation under the theta condition of solvent and temperature, i. e., in cyclohexane at 39°C. Analysis of the data was made by use of Fujita’s equation for the pressure- and concentration-dependent sedimentation. It was found that the sedimentation coefficient at zero concentration and one atmosphere was given as s00=2.00×10−15  M1⁄2 sec, where M is molecular weight. The concentration dependence coefficient k and the pressure dependence coefficient p appearing in the Fujita equation were obtained as k=6.2×10−4  M1⁄2 dl/g, and μ=1.6×10−9 cm2/dyne, respectively. The intrinsic viscosity in the theta solvent was also determined as [η]θ=7.60×10−4  M1⁄2 dl/g.
Electronic Structures and Reactivities of Aliphatic Polycyclo Compounds. I. Fused Three-membered-ring Compounds
Authors: Yonezawa Teijiro , Simizu Kiyoshi , Kato Hiroshi
Published: July 2006

The electronic structures of bicyclo(1.1.0)butane, tricyclo(3.1.0.0)hexane, tricyclo(2.1.0.0)pentane, tricyclo(1.1.0.0)butane, prismane, and spiro(2.2)pentane are studied by the extended Huckel method. The calculated total energies of bicyclo(1.1.0) butanes with various dihedral angles, θ, and bridgehead C–C–H angles, α, show that the most stable configuration of bicyclo-butane is at α=135° and θ=115–120°. It is made clear that the s-nature of the carbon atoms of the C–Haxial and C–Hequatorial depends greatly on the dihedral angle of the two cyclopropane rings. The double-bond character between the bridgehead carbon atoms in the bicyclobutane and its homologues is pointed out. The stabilities of the C–C bonds of prismane are shown to be largely dependent on the angle between the C–H bond and the four-membered-ring plane. The electronic structures of some configurations of spiropentane with different dihedral angles are discussed. The physico-chemical properties of these compounds are briefly investigated.
Infrared Spectra and Conformations of Succinonitrile in Silver and Copper Complexes
Authors: Suzuki Masako , Shimanouchi Takehiko
Published: July 2006

Succinonitrile silver nitrate [Ag(NCCH2CH2CN)]NO3 and succinonitrile disilver nitrate [Ag(NCCH2CH2CN)Ag](NO3)2 were prepared and the infrared spectra down to 60 cm−1 were measured. It was shown that the ligand molecule takes only the trans form in these complexes. The far infrared spectra were also measured for the free succinonitrile ligand at room and liquid nitrogen temperatures and for the copper complex. The assignments of bands for the nitrate ion and the trans and the gauche forms of succinonitrile were given.