bluuebunny/crossref_metadata_2025_split huggingface dataset:
Studies on Nitrogen-Phosphorus Compounds. XXII. The Synthesis and Properties of Phosphoric Aniline Diamide
Authors: Kobayashi Etsuro 
Published: July 2006

Abstract
In order to develop fireproof materials, a new compound, phosphoric aniline diamide, was prepared by employing phosphorus oxychloride, aniline, and ammonia as the starting materials. The conditions for the synthesis and the characteristics of the product have been investigated. Phosphoric aniline diamide can be prepared in the following way: 2 moles of aniline are added to 1 mole of phosphorus oxychloride diluted with chloroform, and the precipitate of aniline hydrochloride, a by-product, is separated from the solvent by filtration. A mixture of phosphoric amide and ammonium chloride is formed by the reaction between an excess of gaseous ammonia and the above filtrate at −10–20°C, and is then separated from the mother liquor. Crude phosphoric amide is extracted from the mixture with ethanol, and subsequent re-extraction with acetone yields the pure product with the formula PONHC6H5(NH2)2. The product thus obtained is composed of a white crystalline powder, soluble in water, ethanol and acetone but insoluble in various organic solvents. The compound shows its own characteristic X-ray diffraction pattern and IR absorption bands. Upon heating, the product melts at about 140°C; condensation occurs by de-ammoniation above 170°C, and conversion into insoluble condensed amidophosphates takes place.
The Estimation of the Electronic Effects of Cyclopropyl and 2,2-Dichlorocyclopropyl Groups
Authors: Kusuyama Yoshiaki , Ikeda Yoshitsugu 
Published: July 2006

Abstract
The normal substituent constant, σ0, and the resonance substituent constant, Δ\barσR+, in the Yukawa and Tsuno treatment of cyclopropyl and 2,2-dichlorocyclopropyl were determined by the ionization of m-, p-substituted phenylacetic acids in 50% aqueous ethanol and by the solvolysis of α-(m-, p-substituted phenyl) ethyl chlorides in 80% aqueous acetone. For cyclopropyl, the obtained σ0 value indicates an inductive electron-attracting behavior, while the Δ\barσR+ value indicates a marked enhancement of the electron-releasing resonance effect on the electron deficient reaction center compared with alkyl groups. A minor resonance contribution was observed for the 2,2-dichlorocyclopropyl group.
Magnetic Susceptibilities of Solid Oxygen-Argon Mixtures
Authors: Mori Yoshihiro , Sakakibara Akira , Inokuchi Hiroo 
Published: July 2006

Abstract
The magnetic susceptibility in solid oxygen-argon mixtures has been obtained as a function of the temperature from 12 K to the melting point. In case of the 95% O2–5% Ar system, the behavior of the magnetic susceptibility was similar to that of pure oxygen except for some dynamical effects caused by the addition of argon to the oxygen lattices. In the composition range between 92% and 66% O2, the appearance of a novel phase, δ, was observed from the magnetic susceptibility measurements; its temperature and concentration dependence was discussed qualitatively on the basis of the crystal structure.
Synthesis and Biological Activity of Peptides Related to Eledoisin. II. Hexapeptide Amides Containing N-Methylamino Acids
Authors: Sugano Hiroshi , Higaki Ko , Miyoshi Muneji 
Published: July 2006

Abstract
Eledoisin-like hexapeptides were synthesized in order to obtain longer-lasting hypotensive analogs. A part of the amino acid of the standard pep tide, H–Lys–Phe–Ile–Gly–Leu–Met–NH2 (1), was replaced by N-methylamino acid. It was found, in these syntheses, that when the C-terminal amino acid of a carboxy component was an N-methylamino acid, a system of dicyclohexylcarbodiimide plus 1-hydroxybenzotriazole was a useful coupling agent. With regard to the hypotensive effect in rabbits, H–Lys–Phe–Melle–Gly–Leu–Met–NH2 (2) and H–Lys–Phe–Ile–Gly–Melle–Met–NH2 (6) show much less activity; H–Lys–MePhe–Ile–Gly–Leu–Met–NH2 (3) and H–Lys–MePhe–Ile–Gly–MeLeu–Met–NH2 (7) show a substantial activity, though weaker than the standard one. On the other hand, H–Lys–Phe–Ile–Gly–MeLeu–Met–NH2 (5) and H–Lys–Phe–Ile–Sar–Leu–Met–NH2(4) show a higher activity than 1. These results indicate that, in some cases, the replacement of an amide bond by an N-methylamide bond without any change in the side chain of amino acid would have an important influence on the activity. The duration of the action of N-methypeptildes synthesized was unexpectedly of the same order of magnitude as that of 1.
Binuclear Metal Complexes. VII. Preparation and Properties of Binuclear Copper(II) and Nickel(II) Complexes of Hydrogen-bridged Macrocycles
Authors: Okawa Hisashi , Tokii Tadashi , Muto Yoneichiro , Kida Sigeo 
Published: July 2006

Abstract
Two types of binuclear copper(II) and nickel(II) complexes, OK-3(H), 3(H)-M2 and [OK-m, 3(H)-M2]ClO4 (m=2 or 3), have been synthesized, where OK-3(H),3(H) is a macrocycle composed of two 2,6-diformyl-4-methylphenol and four hydroxylamine, and OK-m,3(H) is a macrocycle composed of two 2,6-diformyl-4-methylphenol, one diamine (ethylene diamine (m=2) or 1,3-diaminopropane (m=3)), and two hydroxylamine. It was found that a very strong antiferromagnetic exchange interaction is operating between two copper(II) ions for OK-3(H), 3(H)-Cu2 and [OK-2,3(H)-Cu2]ClO4. The complex [OK-2,3(H)-Ni2]ClO4. DMF was found to be a novel-type binuclear nickel(II) complex, in which one nickel (II) ion is diamagnetic and the other is paramagnetic.
Syntheses of Isomaltose, Isomaltotetraose, and Isomaltooctaose
Authors: Koto Shinkiti , Uchida Tetsuo , Zen Shonosuke 
Published: July 2006

Abstract
Ethyl 2,3,4-tri-O-benzyl-6-O-p-nitrobenzoyl-1-thio-α-d-glucopyranoside (I–1) was brominated and subsequently condensed with a deacylated derivative of I–1 in nitromethane in the presence of 2,6-lutidine to give ethyl 2,2′,3,3′,4,4′-hexa-O-benzyl-6′-O-p-nitrobenzoyl-1-thio-α-isomaltoside (I–2) in a 92% yield. These processes were repeated on I–2 to give the blocked tetrasaccharide (I–4) in a 49% yield. Finally, the octasaccharide (I–8) was synthesized in an 11% yield by one more repetition of this reaction cycle. The blocked glycosides, I–2, I–4, and I–8, gave isomaltose, isomaltotetraose, and isomaltooctaose respectively after the sequence of unblocking processes: bromolysis, hydrolysis, methanolysis, and hydrogenolysis.
Hetera-p-carbophanes. I. Hetera-p-carbophanes Containing Two Amide Groups
Authors: Sakamoto Kazuhiko , \={O}ki Michinori 
Published: July 2006

Abstract
Several hetera-p-carbophanes containing two amide groups in the ansa chain were synthesized by the highdilution method. Those which have shorter ansa chains than 15 atoms show no sign of the internal rotation of the benzene ring, even at higher temperatures, whereas that which has the ansa chain of 16 atoms shows no sign of the freezing of the motion, even at lower temperatures. The infrared spectra of these compounds suggest that the amide groups in these compounds exist as the s-cis conformation.
ESR Studies of the Cation Radicals Produced by SbCl5 Oxidation of Some Biphenyls with ortho- and para-Dialkyl Substituents
Authors: Ishizu Kazuhiko , Ohuchi Muneki , Nemoto Fujito , Suga Masao 
Published: July 2006

Abstract
The cation radicals of some alkylbiphenyls such as 4,4′-bitolyl, 4,4′-di-t-butylbiphenyl, and 2,2′, 4,4′, 6,6′-bimesityl, were generated by SbCl5 oxidation in CH2Cl2. The ESR observation was carried out, and the Q, values of the methyl and t-butyl were estimated based on either the theoretical spin density or the experimentally-determined spin density from the 13C-hyperfine splitting. The Q, value of the methyl in the cation radical was found to be 1.5 times that for the anion radical. The t-butyl groups of the cation radical also showed a much larger Q value than that for the anion radical. The perturbation of the spin density due to the steric hindrance was investigated with reference to the prediction of the McLachlan’s MO calculations carried out for the hindered biphenyl. The experimentally-determined spin density derived from the Q value established for the para-derivative can be adequately interpreted on the assumption that the planar character of the biphenyl would be much reduced, contrary to the tendency found for the anion radicals. This effect suggests that a different delocalization of the unpaired electron may be expected between the cation and the anion radical: that is, the unpaired electron brings about a fair bonding on the central 1–1′ bond in the anion radical, but an antibonding for the cation radical, because the odd π-orbital of the cation has its node between the central 1–1′ bond.
The Electronic States of p-Bromanil and Its Anion Radical as Studied by Means of Their Infrared Spectra
Authors: Iida Yôichi 
Published: July 2006

Abstract
The infrared spectra (400–4000 cm−1) were measured with neutral p-bromanil and its anion radical. Appreciable frequency differences between their corresponding bands were observed. The fundamental frequencies were assigned, and the simple Urey-Bradley force fields were determined for both the neutral p-bromanil and its anion radical. The differences in the molecular and electronic structures between these two molecules were discussed on the basis of these results. The half-occupied molecular orbital of the p-bromanil anion radical was found to belong to the b3g irreducible representation.
The Crystal Structure of Trimellitic Acid for the Pseudo-cell
Authors: Takusagawa Fusao , Hirotsu Ken , Shimada Akira 
Published: July 2006

Abstract
The crystal structure of trimellitic acid(benzene-1,2,4-tricarboxylic acid) for the pseudo-cell was determined by the method of X-ray diffraction. The crystal is monoclinic, with the space group of I2/c and with a=15.91, b=61.35, c=8.99 Å, and β=95.4°. The appearence of diffraction patterns strongly indicated the existence of the pseudo-cell with b⁄5 and with the space group of I2/c. The structure of the pseudo-cell was determined by the symbolic addition method. The final R value is 13.6%. There is no intramolecular hydrogen bond between the adjacent carboxyl groups, and one of these carboxyl groups twists greatly out of the plane of a benzene ring so that the repulsion between the oxygen atoms is reduced. Each molecule is joined, through three kinds of hydrogen bonds, with three neighboring molecules. These hydrogen bonds are formed between the carboxyl groups related by the center of symmetry and the two-fold axis. The molecular dimensions and packing obtained by the refinement for the pseudo-cell do not seem to contain unacceptable results.
The Effect of the Temperature on the Mass Spectra of Aliphatic Primary Alcohols and 1-Alkenes. I.
Authors: Hoshino Hiroko , Tajima Susumu , Tsuchiya Toshikazu 
Published: July 2006

Abstract
The decomposition of the (M–18)\underset.+ ion of aliphatic alcohols and that of the M\underset.+ ion of 1-alkenes are studied. The temperature effect of the ion source of a mass spectrometer on the ratios of the intensities of these ions, those of the ions produced from them by C2H4 elimination, and those of the metastable ions for the corresponding fragmentation was measured and was compared with the results to be expected from a simple QET consideration. A discrepancy between the result expected and the experimental result was found for 1-alkenes. In order to clarify the cause of the discrepancy, the photoelectron spectrum was measured for 1-hexanol and for 1-hexene and was assumed to represent the internal energy distribution function, P(E), for each of these substances. Taking the shape of the P(E) into account, the result for 1-alkenes was explained.
Molecular Association and Electronic Spectra of Naphthoic Acids: Formation of an Excimer-like Complex in 1-Naphthoic Acid in Rigid-Glass Matrix
Authors: Kitamura Michio , Baba Hiroaki 
Published: July 2006

Abstract
Absorption and fluorescence spectra of 1- and 2-naphthoic acid (1- and 2-NA) have been studied in a hydrocarbon rigid-glass matrix at 77 K and in the crystal. Each of these acids is associated to form a hydrogen-bonded dimer. On increasing the concentration of 1- or 2-NA, the dimer is further associated to give a higher-order complex that may be assumed to be a tetramer. The fluorescence spectra of the monomer and dimer are in mirror-image relation to their respective absorption spectra in both 1- and 2-NA. When the tetramer of 1-NA is photo-excited, a broad structureless fluorescence emission appears, with the maximum at ca. 7000 cm−1 to the red from the 0–0 band of the dimer fluorescence. The structureless fluorescence spectrum, which has no mirror-image relation to the absorption spectrum of the tetramer, is supposed to originate from an “excimer-like tetramer” of 1-NA. Photo-excitation of the 2-NA tetramer results in a structured fluorescence emission which is considered to come from the simple excited state of the tetramer. The fluorescence lifetimes, quantum yields, and fluorescence-polarization spectra were measured for various molecular species of 1- and 2-NA. The natural fluorescence lifetime of the excimer-like tetramer of 1-NA is evaluated to be 320 nsec, which is 51 times as long as that of the dimer, and the fluorescence from the excimer-like tetramer is polarized mainly along the short molecular axis of the naphthalene nucleus. It is concluded from these observations that the excimer-like tetramer has a symmetrical configuration, with the planes of the constituent dimer molecules parallel to each other, and its fluorescence process is essentially symmetry forbidden.
Circular Dichroism and Absolute Configuration of Triammine(sarcosinate-N-monopropionato)cobalt(III) Chloride and Several Analogues
Authors: Okamoto Ken-ichi , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
cis(O)- and trans(O)-Trianimine(sarcosinate-N-nionopropionato)cobalt(III) salts, which have an asymmetrically coordinated nitrogen atom, were prepared and the cis(O) isomer was optically resolved through its diastereomeric salt with (+)546-(ethylenediaminetetraacetato)cobaltate(III) anion. The less soluble diastereomeric salt produced (+)546-cis(O) isomer of the triammine cation, and its absolute configuration (R) was established from circular dichroism spectrum, referring to the stereochemistry of the several analogous triammine complexes stereo-specifically formed, which contain l-alaninate- and l-prolinate-N-monocarboxylate ligands, where the carboxylate stands for acetate or propionate. Two diastereomeric isomers, R(N)–l(C) and S(N)–l(C), were synthesized for the cis(O)-(l-alaninate-N-monopropionato)triamminecobalt(III) perchlorate salt.
The Synthesis and the Absolute Configurations of Lilac Alcohols, New Naturally Occurring Odorous Ingredients of Lilac Flower
Authors: Wakayama Seiji , Namba Satoshi , Hosoi Kazuo , Ohno Masaji 
Published: July 2006

Abstract
The conversion of racemic linalyl acetate to racemic lilac alcohols has been completed in 5 steps and four diastereoisomers of β,5-dimethyl-5-vinyl-2-tetrahydrofuranethanol were obtained. d-Lilac alcohols were also synthesized from d-linalyl acetate and confirmed to be identical with natural ones. The absolute configurations of lilac alcohol-a, -b, -c, and -d were respectively shown to be (βS, 2S, 5S), (βR, 2S, 5S), (βR, 2R, 5S), and (βS, 2R, 5S) by the chemical and physical evidences.
Branched-chain Sugars. III. Addition of Vinylmagnesium Bromide to 5,6-Dideoxy-1,2-O-isopropylidene-6-C-nitro-3-O-substituted-α-d-xylo-hex-5-enof uranoses
Authors: Iida Takao , Funabashi Masuo , Yoshimura Juji 
Published: July 2006

Abstract
Addition of vinylmagnesium bromide to 3-O-acetyl (1) and 3-O-benzyl (3) derivatives of 5,6-dideoxy-1,2-O-isopropylidene-6-C-nitro-α-d-xylo-hex-5-enofuranose gave the corresponding 5-deoxy-5-C-vinyl derivatives of l-ido-type, of which the configurations were proved by intramolecular cyclization into the corresponding nitrocyclitojs. Conformations of 1 and 3 and that of the transition state in the addition reaction were discussed on the basis of their NMR parameters.
Studies on Aminosugars. XXXVI. Syntheses of 3′,4′-Dideoxy-and 3′,4′,5″-Trideoxyribostamycin
Authors: Ikeda Daishiro , Suzuki Toshihisa , Tsuchiya Tsutomu , Umezawa Sumio , Umezawa Hamao 
Published: July 2006

Abstract
3′,4′-Dideoxyribostamycin and 3′,4′,5″-trideoxyribostamycin have been prepared from ribostamycin via 3′,4′-unsaturation and 5″-iodo-3′,4′-unsaturation intermediates, respectively.
The Reaction of Arylthallium(III) Compounds with Copper(II) and (I) Thiocyanates
Authors: Uemura Sakae , Uchida Satoru , Okano Masaya , Ichikawa Katsuhiko 
Published: July 2006

Abstract
Arylthallium(III) acetate perchlorates reacted with copper(II) thiocyanate to afford aryl thiocyanates in various solvents. The Cu(I) salt was found to be less effective for the thiocyanation. The choice of solvent and the addition of potassium thiocyanate had a significant effect on the yield of aryl thiocyanates. The reaction with the mixture of copper(II) and potassium thiocyanates (1: 1) in dioxane showed the best result. Electron-releasing groups in the aromatic ring accelerated hydrodethallation, yielding aromatic hydrocarbons with a depression of the thiocyanate formation.
Improved Solid-Phase Synthesis of Tryptophan-Containing Peptides. II. Use of Nα-t-Butyloxycarbonyl-Ni-formyltryptophan
Authors: Ohno Motonori , Tsukamoto Sadaji , Sato Shin-ichi , Izumiya Nobuo 
Published: July 2006

Abstract
Ni-Formyltryptophan has proved to be more resistant than tryptophan against oxidation mediated by hydrogen chloride in acetic acid. Nα-t-Butyloxycarbonyl-Ni-formyltryptophan has been synthesized via nonaqueous acylation reaction and used for the solid-phase synthesis of tryptophan-containing peptides, in combination with hydrogen chloride in formic acid as the reagent for cleavage of the t-butyloxycarbonyl group. The validity of the method has been demonstrated, on the basis of several criteria, in the synthesis of the tryptophan-containing octapeptide, Lys–Gly–Val–Leu–Ala–Gly–Trp–Leu.
Molar Volume of Ions
Authors: Hirata Fumio , Arakawa Kiyoshi 
Published: July 2006

Abstract
A formula based on the scaled particle theory of fluids has been derived for the intrinsic volume of ions. Validity ranges of earlier semiempirical formulas are discussed in the light of the formula. Using the theoretical values of the intrinsic volumes of ions, values of volume contraction caused by ion-water interactions are estimated.
X-Ray Photoelectron Spectroscopic Study for the Reaction of Evaporated Iron with O2 and H2O
Authors: Kishi Kosaku , Ikeda Shigero 
Published: July 2006

Abstract
Reactions of evaporated iron with O2 and H2O have been investigated by X-ray photoelectron spectroscopy. Binding energies of Fe2p3⁄2 and Ols electrons were measured during the course of reactions and their variation was discussed in terms of the positive and negative charges of the iron and oxygen of the surface oxide formed, respectively, assuming a simple charge-chemical shift relation. They are compared with the binding energies of the Ols in SiO2 Al2O3, Fe2O3, Cd(OH)2, KOH, and Ni(OH)2 and those of Fe2p3⁄2 in various iron compounds High reactivity of the surface oxide with H2O and the resulting hydroxyl group formation were observed. A rough estimation of the Fe to O atomic ratio of the surface oxide was also carried out from the ratio of the Fe and O peak areas.
The Dissolution of CaMg(SiO3)2 in Acid Solutions
Authors: Sanemasa Isao , Katsura Takashi 
Published: July 2006

Abstract
The dissolution phenomena of synthesized diopside, CaMg(SiO3)2, and a glassy material of the same composition in an acid solution were studied. The results observed in the dissolution of the glass were as follows; the molar concentrations of Ca dissolved in the solution are equal to those of Mg throughout the dissolution of the glass. The rate at which the cations go into solutions are proportional to the surface area up to about a 60% dissolution. The dissolution behavior of silica is similar to that of cations. A residual layer rich in silica is formed, one which is no longer dissolved after the removal of the cations. The results observed in the dissolution of the crystalline diopside were as follows; there is an initial rapid dissolution of the components, followed by another process. The molar ratios of the Ca ions to the Mg ions, and of each cation to silica in the solutions, are larger than those in the solid during the course of the reaction; they are especially large in the initial dissolution stage. An essential feature of diopside dissolution is that the Ca ions are more readily removed from the crystal than are the Mg ions. This fact is also confirmed in the natural diopside crystal. While the rates of the dissolution of the cations are not affected by the concentrations of HCl and HClO4, the concentration of H2SO4 does have an influence. Diopside cannot be dealt with as a single species participating in the heterogeneous reaction because its various components show selective dissolution. The mechanism of the dissolution of diopside will be discussed in connection with its structure.
The Nucleophilic Ring-opening Reactions of α,α′-Dinitrocycloalkanones
Authors: Kobayashi Yoshinari 
Published: July 2006

Abstract
The keto and enolic characters of 2,6-dinitrocyclohexanone (1), 2,6-dinitro-4-methylcyclohexanone (2), and 2,7-dinitrocycloheptanone (3) were spectroscopically investigated and discussed. It was found that the reactions of 1 and 2 with nucleophiles can take either of two courses, depending upon the nucleophiles used: (a) the addition to the enol carbon or carbonyl carbon of the keto form, followed by ring-opening giving 2,6-dinitro- and 2,6-dinitro-4-methyl-hexanoates respectively; (b) the abstraction of the 2- and 6-protons, followed by the formation of the corresponding di-aci-nitronates. Primary alkoxide ions belong to the (a) group, whereas secondary and tertiary alkoxide ions, NH−2, RHN−, and AcO−, belong to the (b) group. The IR and UV spectra of the resultant α,ω-dinitrocarboxylic acid esters were also discussed.
Effect of Pressure on the Rate of Solvolysis. Hydrolysis of 1-Aryl-1-methylethyl Chlorides
Authors: Sera Akira , Miyazawa Toshifumi , Matsuda Tadashi , Togawa Yoichi , Maruyama Kazuhiro 
Published: July 2006

Abstract
The effect of pressure on the hydrolysis rates of 1-aryl-1-methylethyl chlorides were investigated, and the activation volumes, ΔV0\eweq, were calculated. Electron-donating substituents in an aryl group gave less negative ΔV0\eweq values and electron-withdrawing substituents gave more negative ΔV0\eweq values. The observed values of ΔV0\eweq were found to correlate with σ+. These observations are interpreted in terms of the dependence of the degree of solvation at the transition state of the reaction. The temperature dependence of ΔV0\eweq is also discussed.
The Biosynthesis of Geraniol and Citronellol in Pelargonium roseum Bourbon
Authors: Suga Takayuki , Shishibori Tsuyoshi 
Published: July 2006

Abstract
Geraniol and citronellol were biosynthesized from [2-14C]mevalonic acid by the leaves of Pelargonium roseum Bourbon, The degradation of the radioactive specimens revealed that the major radioactivity (70–80%) was located at C-4 in the skeleton derived presumably from isopentenyl pyrophosphate and the rest of the activity at C-8 (and/or C-10) in the moiety from 3,3-dimethylallyl pyrophosphate. The unbalance of labeling was distinct from the result observed for the monoterpenes biosynthesized from the same labeled precursor by the flowers of the rose. A discussion is given on factors causing such a discrepancy in the labeling pattern owing to the difference of the plant and/or the organ. Time-course experiments with the use of [2-14C]mevalonic acid indicated the formation of geraniol prior to citronellol both in the intact plant and in the cell-free extract.