bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of Metal Ions on Reactivity Patterns in the Reactions of 1-Methoxycarbonyl-2-imidazolidinone and Its Derivatives with Butylamine
Authors: Matsumura Noboru , Kawai Hiroshi , Otsuji Yoshio , Imoto Eiji
Published: July 2006

The reactions of 1-methoxycarbonyl-2-imidazolidinone, 3-acetyl-1-methoxycarbonyl-2-imidazolidinone and 1-methoxycarbonyl-cis-perhydrocyclopenta[d]imidazol-2-one with butylamine were studied in the absence and presence of various metal ions. Certain bivalent ions such as Mg2+, Ca2+, and Mn2+ enhanced an electrophilic reactivity of the methoxycarbonyl group and facilitated the transfer reaction of this group to butylamine, especially when the imidazolidinone moiety of substrates bears the methoxycarbonyl group at one N-position and a hydrogen atom at the other N-position. Whereas monovalent ions such as Na+ and Ag+, and bivalent ions such as Zn2+ and Cu2+, had no appreciable effect on the reactivity, and exhibited almost the same reactivity patterns as those observed in the reactions in the absence of metal ions. A possible explanation is given in terms of the stability of coordination complexes which are formed by the interaction between the imidazolidinone moiety of substrates and added ions.
A New Method for Measuring Surface Acidity. The Titration of Silica–Alumina with the Indicator Itself
Authors: Take Jun-ichiro , Kawai Haruyuki , Yoneda Yukio
Published: July 2006

A new method has been proposed for measuring the surface acidity of solid acids. The method involves the titration of a solid acid with the indicator itself in a nonpolar solvent; it determines the number of acid sites from the amount of the indicator chemisorbed at saturation. The titration of silica-aluminas with 4-anilinoazobenzene (pKa=1.5) itself yielded an acid content smaller than the butylamine titration method with the same indicator. This difference in acid content was ascribed to the difference in the base strength of the titrants. Similarly, titration with trans-azobenzene (pKa=−2.9) itself produced an acid content smaller than that with 4-anilinoazobenzene itself.
Stereochemistry of Cobalt(III) Complexes with Thioethers. III. Vicinal Circular Dichroism due to the Chiral Sulfur Donor Atom
Authors: Yamanari Kazuaki , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Two kinds of mixed type cobalt(III) complexes, [(2-aminoethylthio)acetato](l-methioninato)cobalt(III) chloride and [3-(2-aminoethylthio)propionato](l-methioninato)cobalt(III) chloride, have been prepared and chromatographically separated into seven and eight isomers, respectively. The characterization of isomers based on their electronic absorption and 1H NMR spectra leads to the conclusion that there have been obtained four pairs of diastereomers due to the sulfur chirality of the coordinated l-methioninate. The circular dichroism spectra of isomers have been measured and discussed in relation to the absolute configurations. The vicinal CD contribution due to the chiral sulfur atom of l-methioninate has been estimated by applying an additivity rule for the three diastereomeric pairs.
ESR Study of the t-Pentyl Derivative of Yang’s Biradical
Authors: Mukai Kazuo , Yorimitsu Koichi , Mishina Tadashi
Published: July 2006

An asymmetrical t-pentyl derivative of Yang’s biradical was prepared, and the g- and D-tensor values of the biradical were determined from an analysis of an asymmetric ESR spectrum of a frozen solution containing the biradical. The result may be understood by assuming that the benzene ring onto which two pentyl groups are substituted is twisted more than the other two benzene rings. On the other hand, the fluid solution ESR spectrum shows seven hyperfine splittings due to six equivalent meta ring protons in the three benzene rings of the pentyl derivative.
Low-spin Cobalt(II) Complexes with 6,13-Diaryl-1,8-dihydrodibenzo[b,i][1,4,8,11]tetraazacyclotetradecene
Authors: Nishida Yuzo , Sumita Akira , Kida Sigeo
Published: July 2006

The ESR spectra of the title compounds were measured at 77 K. From the results, it was concluded that an unpaired electron is localized in the dyz orbital of the cobalt atom of the complexes.
Photochromism of 2,2,4,6-Tetraphenyl-1,2-dihydro-1,3,5-triazine
Authors: Hayashi Taro
Published: July 2006

2,2,4,6-Tetraphenyl-1,2-dihydro-1,3,5-tri-azine shows temperature dependent photochromism only in a solid state at temperatures above ca. −70 °C under UV(320–380 nm) irradiation, giving several absorption maxima in the visible region, but no change in the IR spectrum. N-Substituted derivatives show no photochromism.
Reaction of Dioxygen Complexes with Catechols
Authors: Muto Shigeaki , Tasaka Kazuaki , Kamiya Yoshio
Published: July 2006

The square planar dioxygen complexes MO2(PPh3)2(M=Pt, Pd) reacted with catechols at low temperature to give H2O2 and the corresponding catecholato complexes, characterized by their physical properties, in high yields. A similar treatment of PtO2(PPh3)2 with o-substituted anilines afforded the corresponding adducts and H2O2 in moderate yields.
Friedel-Crafts Reaction of Benzene with 2-Phenylbutanedioic Anhydride
Authors: Hashimoto Iwao , Takatsuka Ryozo
Published: July 2006

The AlCl3-catalyzed acylation of benzene with 2-phenylbutanedioic anhydride was found to give a mixture of 3-benzoyl-2-phenylpropanoic acid, isomeric 3-benzoyl-3-pehnylpropanoic acid, and 3-oxoindan-1-carboxylic acid. The distribution of the products was affected markedly by the amount of AlCl3 or solvents used.
An Efficient Synthesis of Bicyclo[3.1.0]hex-3-en-2-one
Authors: Oda Masaji , Kanao Yoshinori , Kasai Masaji , Kitahara Yoshio
Published: July 2006

Bicyclo[3.1.0]hex-3-en-2-one is synthesized in fair yield in five steps from 4-cyclopentene-1,3-dionefuran Diels-Alder adduct.
The Structure of Sendanolactone, a New Triterpenoid from Melia azedarach L. var. japonica Makino
Authors: Ochi Masamitsu , Kotsuki Hiyoshizo , Tokoroyama Takashi , Kubota Takashi
Published: July 2006

Sendanolactone, a new tetracyclic triterpenoid from the bark of M. azedarach  L. var. japonica Makino, was determined as 3,6-dioxo-13α,14β,17α-lanosta-7,24-dien21,16β-olide on the basis of chemical and spectroscopic evidence.
A Convenient and General Preparation of Diphenyl Tellurium Dicarboxylates
Authors: Tamagaki Seizo , Hatanaka Isao , Kozuka Seizi
Published: July 2006

A number of diphenyl tellurium dicarboxylates were readily prepared from diphenyl telluroxide and carboxylic acids or anhydrides. Some of them were also derived through the carboxylate exchange from readily available tellurium carboxylates.
Alicyclic Terpenoids from Cyclocitryl Phenyl Sulfides. V. A Synthesis of Ferruginol
Authors: Torii Sigeru , Uneyama Kenji , Hamada Kazuhide
Published: July 2006

Ferruginol a precursor for taxodionesynthesis, was prepared by the coupling of C(10) units between 2-(phenylsulfonylmethyl)-1,3,3-trimethylcyclohexane and 3-isopropyl-4-methoxybenzyl bromide followed by desulfonation and acid-catalyzed cyclization.
Exciplex and EDA Complex Fluorescence in 1,4-Dicyanonaphthalene with Alkylbenzenes and Alkylnaphthalenes
Authors: Itoh Michiya , Furuya Shu-ichi , Okamoto Toshihiko
Published: July 2006

The exciplex (at room temperature) and EDA complex (at low temperature) fluorescence was observed in 3-methylpentane solution of 1,4-dicyanonaphthalene with several alkylbenzenes and alkylnaphthalenes. The fluorescence behavior provides evidence for an identical fluorescent state of the exciplex and EDA complex.
NMR Studies of Picolyl-type Carbanions. IV. Anions Produced by Reactions of 2-Substituted Pyridines with Butyllithium
Authors: Konishi Kazuyori , Takahashi Kensuke
Published: July 2006

The 13C and 1H NMR spectra of 2-pyridylmethyl (α-picolyl), 2-pyridylamino, 2-pyridyloxy, and 2-pyridylthio anions were observed in polar solvents with lithium as a counter ion. The chemical shifts are compared with the electron densities calculated using the PPP and CNDO/2 MO methods. A linear relationship was obtained between the 13C chemical shifts and π-electron densities. The charge distributions on the anions are discussed, and it is found that the 2-pyridylamino anion and its methyl derivatives can be regarded as delocalized anions with the same significance as a series of picolyl anions.
Application of Infrared ATR Spectroscopy to Liquid Crystals. I. Surface-Induced Orientation in Thin Films of Nematic MBBA
Authors: Hatta Aritada
Published: July 2006

Infrared dichroism of nematic liquid N-(p-methoxybenzylidene)-p-butylaniline (MBBA) was measured using a conventional transmission method and an ATR method. In the former, KBr windows were used as substrates. The degree of orientation order of the homogeneous structure, which was achieved by a rubbing procedure, was obtained to be S=0.40. Using the measured dichroic ratios, the angles between the transition moments and the long axis of the molecule were calculated. The calculated values are in satisfactory agreement with the molecular conformation already suggested. In the ATR method, In2O3-coated glass plates were used as substrates. Rubbing of the In2O3 surface gave a uniform homogeneous orientation with an S value of 0.57. An In2O3 surface treated with dimethyldichlorosilane gave a homeotropic texture with an S value of 0.53. The directions of the transition moments relative to the long axis of the molecule closely agreed with those obtained from transmission spectra.
Synthesis of Alanyl-1-aminoethanesulfonic Acid
Authors: Shiba Tetsuo , Miyoshi Kenichi , Kusumoto Shoichi
Published: July 2006

For the purpose of the verification of an expectation that the structural analogs of d-alanyl-d-alanine which participates in the biosynthesis of cell wall peptides might inhibit the growth of microorganisms, alanyl-1-aminoethanesulfonic acid was synthesized by the mixed anhydride method. Four diastereomers were separated and their absolute configurations were deduced on the basis of X-ray analysis. None of these dipeptide analogs and their benzyloxycarbonyl or t-butoxycarbonyl derivatives showed appreciable activity against E. coli.
The Behavior of Aqueous Solution of Sodium Deoxycholate in Capillary Flow
Authors: Sugihara Gohsuke , Tanaka Mitsuru , Matuura Ryohei
Published: July 2006

Primary micelles form secondary, polymer-like aggregates in a capillary flow of aqueous solution of sodium deoxycholate (SDC). The formation of the polymer-like aggregate is promoted by mechanical action, degradation being simultaneously caused by shearing stress. The viscosity of the SDC solution in the capillary flow attains equilibrium value between polymerization and degradation. The viscosity changes a great deal with the time of observation and pH. Under given conditions the SDC solution behaves as a non-Newtonian fluid obeying a power-law.
Comparison of Experimental and Calculated Oscillator Strengths for Condensed Ring Compounds
Authors: Yoshinaga Tetsutaro , Hiratsuka Hiroshi , Tanizaki Yoshie
Published: July 2006

The electronic absorption spectra of eighteen aromatic condensed ring compounds (C2v or D2h) were studied by means of comparison between the calculated and experimental results in terms of three fundamental factors: the electronic transition energy, the direction of the electronic transition moment, and the oscillator strength. The three experimental factors were obtained from the component spectra polarized to the long and short axes of the molecule, which were determined by means of the dichroism analysis technique. The calculated oscillator strengths were obtained by the dipole-length, dipole-velocity, and mixed-dipole methods. From the comparison between experimental and calculated results, it was found that the mixed-dipole method gives the best fit of the values to the experimental ones.
ESR Studies of the Photoreduction of Quinones. II. The Reinter-pretation of Semiquinone Intermediates from Halogenated p-Benzoquinones in Ethanol
Authors: Kambara Yoshihiko , Yoshida Hiroshi , Rånby Bengt
Published: July 2006

A reinterpretation was made of the electron spin resonance spectrum of semiquinone intermediates during the photolysis of a flowing solution of tetrachloro-p-benzoquinone (chloranil) in ethanol. The photoinduced spectrum with a width of 0.06 mT with an unresolved hyperfine structure was found to be identical with the spectrum of the semiquinone anion generated by reducing chloranil in an alkaline ethanol solution. This and other observations indicated that the photoinduced spectrum was due to the chloranil semiquinone anion formed primarily by the one-electron transfer to chloranil from the solvent ethanol, rather than to the semiquinone radical. The photoinduced one-electron transfer reaction was found, though qualitatively, to proceed more efficiently for chloranil and fluoranil, with a larger electron affinity, than for p-benzoquinone and dichloro-p-benzoquinones.
Molecular Structure of 2-Chloropropane, as Determined by a Combined Use of the Electron Diffraction Data and the Spectroscopic Moments of Inertia
Authors: Iijima Takao , Seki Schigenori , Kimura Masao
Published: July 2006

The gas-phase molecular structure of 2-chloropropane, (CH3)2CHCl, has been investigated by means of electron diffraction and by a joint analysis of the diffraction results and the spectroscopic moments of inertia. The structure parameters, distances in rg and angles in \varphiav, were determined (with parenthesized limits of error) to be as follows; C–Cl 1.812(1) Å, C–C 1.527(1) Å, C···Cl 2.720(2) Å, C–H 1.104(4) Å, ∠CCC 112.7(4)° and ∠HCH 108.5(8)°. The CCHsec angle was assumed to be 109.8(20)°. The present results, together with the data for other molecules, confirmed a systematic elongation of the C–Cl rg-distance in the series of methyl, ethyl, isopropyl, and t-butyl chlorides.
Deacylations and Syntheses of Some 9-Acylfluorenes
Authors: Kimura Takao , Minabe Masahiro , Tsubota Motohiro , Suzuki Kazuo
Published: July 2006

Deacylations of substituted 9-acetyl-, 9-propionyl-, 9-benzoyl-fluorene, and 9-fluorenyl 9-methyl-9-fluorenyl ketones were studied; the reactivity of deacylation was enhanced by the substitution of the 9-hydrogen atom on 9-acetylfluorene. The reaction of 9-acetylfluorene with ethyl nitrate afforded 9-aci-nitrofluorene.
A Study of the Transport of Tetraalkylammonium Ions through Ion-exchange Membranes
Authors: Inenaga Kiyotoshi , Yamauchi Akira , Kimizuka Hideo
Published: July 2006

The membrane potential and conductance of the cation-exchange membrane-aqueous quaternary tetraalkylammonium chloride systems have been measured by using NH4+, tetramethyl-(Me4N+), tetraethyl-(Et4N+), tetrapropyl-(Pr4N+), and tetrabutylammonium ions (Bu4N+). The potential change in the concentration cell with these salts was about 58 mV for a tenfold change of concentration. The membrane conductance in the concentration cell increased with the concentration. The membrane permeability, as estimated from the potential and conductance data, was in the order of NH4+>Me4N+>Et4N+>Pr4N+>Bu4N+; it is proportional to the geometric mean of the activities of exterior solutions. The effective pore size of the membrane was deduced from the conductance data and found to be ca. 10 Å. The selective permeation coefficient has been determined from the potential data of the two- and multi-ionic systems. The selectivity data obtained with the two-ionic system were in agreement with those obtained with the multi-ionic system. The selectivity increased with the chain length of the cation, in contrast to the reversed order of the membrane permeability in the concentration cell. This was attributed to the decreasing mobility with the increasing chain length.
Ultraviolet Spectral Study of o- and p-(Halomercurio)phenols
Authors: Yadav P L , Jha N K , Ramakrishna V
Published: July 2006

The ultraviolet spectra of o- and p-(halomercurio)phenols, o- and p-OHC6H4HgX(X=F, Cl, Br, or I) have been recorded in ethanolic solution and λmax and logεmax have been recorded. The spectra of these compounds have been interpreted in terms of the correlation with the spectra of benzene. HgX group is shown to be having electron-withdrawing effect on the benzene ring. Variation in the values of λmax and logεmax on changing from o- to p-derivative for a particular (halomercurio)phenol and on changing the halogen attached to mercury has been explained.
Studies on the Mechanism and Kinetics of Propylene Oligomerization and Hydrooligomerization on Zeolites
Authors: Hassan Shawky M , Panchenkov G M , Kuznetsov O I
Published: July 2006

The propylene conversion process has been studied in the presence of synthetic zeolites of different types and metal ions. The NiX zeolite is selective for the oligomerization of propylene. On the zeolites of different other metal ions, the hydro-oligomerization process took place. It has been found that the obtained 3-methylpentenes are primary products of the propylene oligomerization. A scheme mechanism has been proposed assuming an intermediate of a cyclobutane derivative. The mechanism explains the formation of all the obtained products of propylene conversion on the synthetic zeolites.
Multiple Relaxation Processes in Long Chain Molecules at Microwave Frequencies
Authors: Purohit H D , Sharma H S
Published: July 2006

The permittivity ε′ and dielectric loss ε″ of octanoyl, undecanoyl, and lauroyl chlorides have been measured in benzene for five different concentrations varying from 0.02 to 0.10 wt fraction at three different microwave frequencies, viz. 3.31, 9.83, and 26.90 GHz at 35 °C. The static permittivity ε0 at 100 kHz and the high frequency limiting permittivity ε∞ have also been measured at the same temperature. The permittivity and dielectric loss at different frequencies have been plotted against concentration and their slopes have been used to draw normalised complex plane plots between (a′–a∞)/(a0–a∞) and a″/(a0–a∞) for these compounds. Such plots show a skewed arc dielectric behaviour. The values of distribution parameter β, characteristic relaxation time τ0, average relaxation time τav, and dipole moment μ have been reported for the first time. The relaxation mechanism in these three molecules has been explained on the basis of multiple relaxation processes.
Preparation and Properties of the Uni- and Binuclear [Co(III)N2O4] Type Complexes Containing (S)-2-Amino-1-propanol
Authors: Nishide Toshikazu , Saito Kazuo
Published: July 2006

Reactions of (S)-2-amino-1-propanol (S-praH) with the tricarbonatocobaltate(III) solution gave binuclear complexes bridged by carbonates, or carbonate and hydroxide. The carbonate was replaced by oxalate (ox2−) to give binuclear complexes [(S-praH)2Co(ox)2Co(S-praH)2]2+ and uninuclear trans(N)cis(O)-[Co(ox)(S-pra)(S-praH)]. Another uninuclear complex [Co(ox)(S-praH)2]+ was obtained by direct synthesis from S-praH and cobalt(II) acetate by oxidation with lead dioxide. Column chromatography with SP-Sephadex C-25 was useful for separating the geometrical isomers, which were identified by PMR, IR, visible, and UV absorption spectra. Their circular dichroism (CD) spectra changed depending on pH of the aqueous solution. All the S-pra− chelates have δ-conformation, which is characterized by an intensive plus CD component in the 25000 cm−1 region, regardless of the skeletal structure of the complexes.
Synthesis of Taxodione, Royleanone, Cryptojaponol, and Methyl 11-Hydroxy-12-methoxy-7-oxoabieta-8,11)13-trien-18-oate
Authors: Matsumoto Takashi , Ohsuga Yasuo , Harada Shogo , Fukui Kenji
Published: July 2006

Oxidation at the C-11 position of methyl 12-hydroxyabieta-8,11,13-trien-18-oate (II) and ferruginol (XXXII) were successfully carried out using benzoyl peroxide, and the resulting phenols (VII and XXXVII) were further converted into taxodione (III), royleanone (IV), cryptojaponol (V), and methyl 11-hydroxy-12-methoxy-7-oxoabieta-8,11,13-trien-18-oate (VI).
Complex Formation of Silver(I) Ion with Some Aliphatic Diamines
Authors: Ohtaki Hitoshi , Cho Kenji
Published: July 2006

Complex formation of silver(I) ion with 1,3-propanediamine and 1,4-butanediamine has been studied poten-tiometrically at 25 °C in 3 mol dm−3 LiClO4 aqueous solution. Some additional experiments have been carried out in the system of silver-1,2-ethanediamine of large diamine/Ag ratios, the system having been examined in a previous work at small diamine/Ag ratios. Over the pH range of 6—10.4, the emf data obtained in the silver-diamine solutions could be explained in terms of the formation of the following complexes (L denotes the free diamine molecule): In a solution of low pH (pH=6—8), the AgHL2+ and AgH2L23+ complexes are formed. In an alkaline solution, the AgL+, Ag2L22+, and AgL2+ complexes are formed, and the relative amounts of the complexes depend on the concentrations of the metal and ligand (L) and also the ratio of these concentrations. The Ag(OH)L complex becomes a main species at the highest pH examined. In some cases the formation of the AgHL22+, Ag2HL23+, and Ag2L2+ complexes is suggested from the graphical or computer analysis of the data, but the formation constants of the complexes are rather uncertain. Over the whole pH range examined, the AgHL2+, AgH2L23+, AgL+, and Ag2L22+ complexes are predominant in all the systems.
Phthalimides. I. Base-catalyzed Lossen Rearrangement and Acid-catalyzed Beckmann Rearrangement with N-(Arylsulfonyloxy)phthalimides
Authors: Fahmy A F M , Aly N F , Nada A , Aly N Y
Published: July 2006

N-(Arylsulfonyloxy)phthalimides undergo base-catalyzed Lossen rearrangement with amines, and amino acids to give N,N′-diaryl ureas and amine salts. They behave similarly with phenylhydrazine in alcohol to give a mixture of N-hydroxyphthalimide and phenylhydrazine salts. However, N-(arylsulfonyloxy)phthalimides undergo isomerization followed by Beckmann rearrangement to give a mixture of 4-aryl-1H-2,3-benzoxazin-1-ones and diarylsulfones.
Thermally Dissociative Degradation of Polymers Containing Dicyclopentadiene Ring in Main Chains
Authors: Miura Masatoshi , Akutsu Fumihiko , Hirose Shigeo , Ikeno Yoshiyuki , Nagakubo Kuniharu
Published: July 2006

Polymers containing dicyclopentadiene units in their main chain were prepared by the polycondensation of dicyclopentadienedicarbonyl dichloride with bis(p-hydroxyphenyl) ether or 2,2-bis(p-Khydroxyphenyl)propane. Thermal analysis showed that the dicyclopentadiene units dissociate reversibly. The results of thermal degradation in a nitrobenzene solution indicate that a reversible degradation occurs at 10% concentration of the polymer, and an irreversible one at concentration below 1%. The activation energy of the dissociation of dicyclopentadiene units in the main chain of the polymer was estimated to be 30 kcal/mol.
Kinetic Study of the Reactions of Phenacyl Benzoates with Trialkyl Phosphites
Authors: Hashimoto Shizunobu , Furukawa Isao , Tatsumi Takao
Published: July 2006

The reactions of phenacyl benzoates, X–C6H4COCH2OCOC6H4–Y (1a–i), with trialkyl phosphites (2a–c) giving dialkyl 1-arylvinyl phosphates (3a–d) in high yields were studied kinetically using the GLC technique. The overall reactions are second order, and exhibit a moderate solvent effect and catalysis upon the addition of certain organic acids. The activation energy, Ea=16.5 kcal/mol, and entropy, ΔS\eweq=−38.5 e.u., were obtained from the reaction of 1a with 2b, and the ρ value obtained using σ for reactions of the two series of 1a with 2b was ρx=3.4 and ρY=1.0, respectively. The reactivity of 2 in this reaction is markedly increased in the order, Me<Et<i-Pr. These and other data accumulated support a mechanism for this reaction involving a ratedetermining addition of phosphorus atoms in 2 to the carbonyl carbon of the phenacyl group followed by rearrangement of the phosphorus moiety to the carbonyl oxygen of the phenacyl group.
Steric Effects of Alkyl Substituents on the N–H Stretching Absorptions and Rotational Isomerism of N,N′-Dialkylthioureas
Authors: Mido Yoshiyuki , Yamanaka Takashi , Awata Ryoichi
Published: July 2006

The fundamental N–H stretching absorptions of twenty nine N,N′-dialkylthioureas were observed in dilute solutions. The observed frequencies were classified into five groups assignable to the out, three different types of the trans, and the cis forms. The steric hindrance between the bulky t-butyl group and the thiocarbonyl sulfur, which is larger than for N,N′-dialkylureas, was suggested to cause the out form. Dialkylthioureas of RTUtB type seem to exist to a great extent in the trans-out conformation in solutions. It is suggested that it is not the N–H group with the bulky t-butyl group but the N–H group in the opposite part which is out of the skeletal plane. The energy difference between the out and the trans forms was found to be ΔH=430±100 cal mol−1.
The Glow-discharge Reactions of Pyrrole, Pyrrolidine, and Butylamine
Authors: Kikkawa Sh\={o}ichi , Nomura Masakatsu , Hosokawa Noritaka
Published: July 2006

The glow-discharge reactions of pyrrole, pyrrolidine, and butylamine were carried out. Pyrrolidine produces a complex mixture of products, the most prevalent of which is (Remark: Graphics omitted.) (R: H, CH3, and C2H5), and butylamine yielded primarily CH3(CH2)3N=CHR (R: CH3, C2H5, and C3H7) along with CH3(CH2)3NHCH2CN, whereas pyrrole afforded a mixture of acrylonitrile, crotononitrile, benzene, α-methylpyrrole and β-methylpyrrole, together with large amounts of HCN. The formation of characteristic products, α-(1-pyrrolidinyl) nitrile derivatives with pyrrolidine, and the yield of butylaminoacetonitrile with butylamine can be explained by considering the formation of a resonance-stabilized α-cyanoalkyl radical as the most probable intermediate which attacks a nitrogen atom of pyrrolidine and that of butylamine or which recombines with pyrrolidine-N-radical and butylamine-N-radical.
The Oxidative Solvolysis of Durohydroquinone Monobenzoates. A Study of the Mechanism
Authors: Takagi Makoto , Tazaki Masato , Matsuda Tsutomu
Published: July 2006

Durohydroquinone mono(p-substituted benzoate)s (1a–1e) were oxidized by DDQ, in CH3OH/CH2Cl2 at room temperature. The products were duroquinone dimethyl acetal 4 and p-substituted benzoic acids (5a–5e). None of the methyl esters 3 was formed. The details of the mechanism of a series of reactions, which start with the one-electron oxidation of 1, is elucidated by the isolation and characterization of the intermediates as well as by a kinetic study in an acetonitrile solution. The relation between the mode of oxidation, whether it is a one-electron or two-electron process, and the activation of the acyl group was explicitly discussed in terms of the mechanism. Two-electron oxidation is suggested to offer a better chance for acyl activation. Some generalization of the mechanism is made for other oxidation-induced acyl, phosphoryl and sulfuryl activating systems.
The Temperature and Solvent Effects on the AlCl3-catalyzed Cyclization of 3,3′-Diphenyl-2,2′-biindenyl-1,1′-dione
Authors: Toda Fumio , Todo Yozo
Published: July 2006

Upon the AlCl3-catalyzed cyclization of the title biindenone (1) into benz[c]indeno[2,1-a]fluorene-13,14-dione (2) and 3,3′: 3,3′-di(o-phenylene)-2,2′-biindenylidene-1,1′-dione (3), the 2:3 ratio increased when the reaction temperature was raised and decreased when the polarity of the solvent was increased.
Studies of Pyrazines, I. Pyrolyses of Substituted Pyrazines and Their Thermal Stabilities
Authors: Konakahara Takeo , Takagi Yukio
Published: July 2006

The pyrolyses and thermal stabilities of 2,5-dialkylpyrazines (1a–e), 2,5-diethoxypyrazine (2), chloropyrazine (3), alkoxypyrazines (4a–c), alkylthiopyrazines (5a, b), and alkylaminopyrazines (6a–d) were studied by means of a mass spectrometer, by which the pyrolysates in the sample reservoir were analyzed. The temperature dependence of the molecular ions and/or fragment ions was also discussed. The thermal dehydrogenation from two α-methine groups makes the 1d molecule thermally sensitive. The other 2,5-dibutylpyrazines were more stable than it, except for the t-butyl derivative, 1e. Hydroxy- and aminopyrazine, 4a and 6a, were very stable. The alkoxypyrazines, 4b and 4c, and alkylthiopyrazines, 5, underwent the thermal elimination of olefine to yield hydroxy- and mercaptopyrazine respectively. The latter disproportionated to form dipyrazinyl sulfide (11). At 280 °C, no analogous reactions of alkylaminopyrazines 6b–d could be observed. The relative thermal stabilities of the compounds were as follows:

2, 4a, 6a, 4b>1c>1e>1b>6c, 5a>3>6b>1d>1a>6d, 5b>4c
Preparation and the Properties of π-Allylic Palladium(II) Complexes of Amino Acid
Authors: Nakagawara Yoshihiro , Kikukawa Kiyoshi , Takagi Makoto , Matsuda Tsutomu
Published: July 2006

The preparation of π-allylic and related organopalladium(II) complexes with amino acid anions as bidentate ligands is described. The complexes were characterized by means of 1H NMR.
Relations between the Thermodynamic Properties of Alkali Halides at the Melting Point
Authors: Kanno Hitoshi
Published: July 2006

Two new empirical formulas are presented for alkali halides at the melting point. There is a set of linear relations between the initial slope of melting curve (dTm⁄dP) and the solid volume (Vs) for the sequences LiX, NaX, KX, and RbX (X=F, Cl, Br, and I).
Studies of Lignoids in Lauraceae. III. A New Lignan from the Heart Wood of Cinnamomum Camphora Sieb.
Authors: Takaoka Daisuke , Imooka Minoru , Hiroi Mitsuru
Published: July 2006

From the heart wood of Cinnamomum Camphora Sieb., a new lignan, (−)-trans-2-(3,4-dimethoxybenzyl)-3-(3,4,5-trimethoxybenzyl)butyrolactone [I] and 3-hydroxy-5,7-dimethoxy-3′,4′-methylenedioxyflavan [IV], were isolated, and their structures were determined.
Preparation of Mannich Bases from 6-Methoxy-2H-pyran-3(6H)-one and Its Epoxide
Authors: Torii Sigeru , Tanaka Hideo , Takao Hisasi
Published: July 2006

4-Morpholinomethyl-2H-pyran-3(6H)-ones 3 and 8 were prepared directly from 6-methoxy-2H-pyran-3(6H)-one (1) and its epoxide 4 by treatment with morpholine and aqueous 37% formalin in methanol in 70–88% yield. The mechanisms of the reaction have been discussed on the basis of the intermediates 5,6-dimethoxytetrahydropyran-3-one (2), 2,6-dimethoxy-5-hydroxytetrahydropyran-3-one (5), 2,6-dimethoxy-2H-pyran-3(6H)-one (6), and 2,5,6-trimethoxytetrahydropyran-3-one (7).
Aryl Alkanehydrazonates and Their Thio Analogs. Synthesis of Some 2-Alkyl Derivatives of 4H-1,3,4-Benzoxadiazines and 4H-1,3,4-Benzothiadiazines
Authors: Shawali Ahmad Sami , Hassaneen Hamdi Mahmoud
Published: July 2006

Synthesis of some p-nitrophenyl alkanethiohydr azonates, RC(SC6H4NO2-p)=NNHC6H3BrNO2(2, 4−), and p-nitrophenyl alkanehydrazonates, RC(OC6H4NO2p=NNHC6H3BrNO2(2,4−) is described. Upon treatment with triethylamine in ethanol at reflux the thiohydrazonates give directly 2-alkyl-4-(p-nitrophenyl)-7-nitro-4H-1,3,4-benzothiadiazines, whereas the hydrazonates yield the hydrazides, RCONHN(C6H4NO2-p)C6H3BrNO2(2,4−). The latter hydrazides can be cyclized, under stronger basic conditions, into 2-alkyl-4-(p-nitrophenyl)-7-nitro-4H-1,3,4-benzoxadiazines by displacement of the 2-bromine atom.
A Study of the Behavior of Surface Oxygen of V2O5 Catalysts by the Use of the 18O-Tracer
Authors: Kera Yoshiya
Published: July 2006

By the use of highly concentrated 18O-carbon dioxide, both the rate of the isotopic exchange of CO2 and the surface oxygen of a powderd V2O5 catalyst and that of the isotopic equilibration of CO2 on the surface were determined simultaneously in the temperature range from 330 to 450 °C. The rate of the isotopic exchange on the thin-plate crystallines, in which the (010) plane of V2O5 crystal was mainly exposed, was also determined. The equilibration rate was 30–40 times faster than the exchange rate. The exchange process on the thin-plate crystallines was found to be extremely rapid, although such a phenomenon has never been found on the powdered catalyst. Based on these results, the relationship of the reaction steps of the isotopic exchange and the isotopic equilibration with those on the triangular scheme of CO-oxidation, previously proposed, was discussed in detail. A small cycle of alternate reduction-oxidation on the top of the surface, especially on the (010) plane, was conclusively confirmed.
The Determination of the Critical Volume for the Free Motion of Solute Entities in an Aqueous Solution
Authors: Fujiwara Shizuo , Nagashima Kozo , Morita Hiroshi , Kanaoka Yasushi
Published: July 2006

A certain volume of a solution, (20–30 Å)3 per unit of solute entity, designated the “molecular space,” is assigned as the necessary volume for the free motion of the solute. By the use of ESR, the actual size of the molecular space has been determined for the cupric ion and 2,2,5,5-tetramethyl-3-carbamoylpyrollidin-1-oxyl. It is pointed out that the concentrations of the important solutions in nature, such as sea water or human serum, may correspond to the moleuclar space of ions.
31P Magnetic Relaxation in Polynucleotides
Authors: Akasaka Kazuyuki , Yamada Atsuko , Hatano Hiroyuki
Published: July 2006

Phosphorus-31 nuclear spin-lattice relaxation times and nuclear Overhauser enhancement upon nonselective proton saturation were measured on polyriboadenylic acid, polyribocytidylic acid, and polyribouridylic acid. A method is described to separate dipolar contribution from the contribution of chemical shift anisotropy for the phosphorus relaxation by the combined use of T1 and NOE data. Chemical shift anisotropies (δ⁄⁄−δ⊥) of phosphorus in these polynucleotides in solution are estimated to be in the range 120–165 ppm. The molecular motion of the phosphorus moiety becomes faster in the order, poly(A)<poly(C)<poly(U), the thermal activation processes being characterized by single activation energies, i.e., 5.1, 5.3–6.0, and 7.2–8.1 kcal/mol for poly(U), poly(C), and poly(A), respectively.
Electronic States of the Crystals of TCNE Complexes with Hexamethylbenzene, Acenaphthene, and Dibenzofuran
Authors: Tanaka Masashi
Published: July 2006

The polarized reflection spectra were measured on crystals of tetracyanoethylene and its charge-transfer complexes, and the absolute intensity of the absorption parallel to the crystalline axes has been obtained by the Kramers-Kronig transformation. The charge-transfer degree and the stabilization energy in the ground state were estimated for each complex by analyzing the charge-transfer bands in the crystalline state. In the TCNE–hexamethylbenzene(HMB), acenaphthene, and dibenzofuran complexes, the charge-transfer degrees are 9.05, 12.3, and 4.95% respectively in the ground state.
The Two-Photon Excitation Spectrum of Phenanthrene Crystal
Authors: Otokozawa Hiroshi , Inomata Shigehiro , Mikami Naohiko , Ito Mitsuo
Published: July 2006

The two-photon excitation spectrum of phenanthrene crystal was measured and compared with the corresponding usual one-photon absorption spectrum. It was found that the two-photon spectrum consists of a one-photon like system and a system characteristic of a two-photon process. The vibronic couplings in phenanthrene were discussed on the basis of the observed results.
A Method for the Analysis of Halogenated Organic Compounds in Tap Water by Means of Mass Fragmentography of GC-MS
Authors: Fujii Toshihiro
Published: July 2006

A simple, sensitive and practical method for the halogenated organic compound analysis of tap water is reported. A pentane extraction procedure using a ten fold increase in concentration by volume (without further concentration) followed by mass fragmentography of GC-MS was used. As little as 0.05 ppb concentration of each compound was detectable. Five simple halogenated organic compounds, including CCl4 and CHBr3 whose concentrations are relatively small, were determined for tap water in Japan.
The Synthesis of α-Aminonitriles Starting from the Corresponding Amino Acids. I. Use of o-Nitrophenylsulfenyl as an N-Protecting Group
Authors: Kawashiro Katsuhiro , Yoshida Hideyuki , Morimoto Shiro
Published: July 2006

N-o-Nitrophenylsulfenylamino acid amides of glycine, alanine (Dl and l), leucine (Dl and l), methionine (Dl), phenylalanine (Dl and l), and proline (l) were dehydrated in POCl3-pyridine. The N-protected α-amino-nitriles obtained were treated with anhydrous HCl affording the corresponding α-aminonitrile hydrochlorides. The optical purity of the l-α-aminonitriles was well retained.
Proton Magnetic Resonance Studies of cis-trans Equilibria of Some N-(2,5-Dichlorophenyl)-3-aminocrotonamides
Authors: Kondo Michio
Published: July 2006

The 1H NMR spectra of 3-(alkylamino)crotonamides indicate that these substances exist in solution as a mixture of the geometric isomers, cis and trans, in which the chelated cis form is predominant. Unsubstituted 3-aminocrotonamide appears to exist in the cis form only, and N,N-disubstituted derivatives in the trans form. In the case of 3-(alkylamino)crotonamide it is found that the cis-trans equilibrium is solvent dependent and that the apparent rate of interconversion between the isomers is very slow in chloroform-d, fast in dimethyl-d6 sulfoxide, and intermediate in acetone-d6 and methanol-d4. It seems that the cis-trans equilibrium is almost independent of both temperature and concentration, and that the replacement of the olefinic H by D proceeds through enamine\ightleftharpoonsimine tautomerization.
Stereochemical Studies of the Electrolytic Reactions of Organic Compounds. IV. Electrolytic Reduction of Optically-active 1-Pyridylalkanols to the Corresponding Substituted-alkyl Pyridines
Authors: Nonaka Tsutomu , Ota Tetsuro , Fuchigami Toshio
Published: July 2006

The mechanism of electrolytic reduction of 1-pyridylalkanol to the corresponding substituted-alkyl pyridine was examined by electrolyzing several optically-active 1-pyridylalkanols in an aqueous sulfuric acid solution in the vicinity of a mercury cathode. The alkyl pyridine from 1-(2-pyridyl)alkanol showed optical rotation, while that from 1-(4-pyridyl)alkanol was almost racemized.
The Ullmann Condensation Reaction of Haloanthraquinone Derivatives with Amines in Aprotic Solvents. II. The Presence of an Induction Period in the Condensation with 2-Aminoethanol
Authors: Arai Sadao , Hida Mitsuhiko , Yamagishi Takamichi , Ototake Satoshi
Published: July 2006

An induction period was present in the Ullmann condensation reactions of 1-bromoanthraquinone(AQBr) with 2-aminoethanol(AE) in the presence of CuBr or CuI in aprotic solvents under a nitrogen atmosphere, while there was no induction period in the reaction systems of 1-iodoanthraquinone(AQI)–AE–CuBr, AQI–AE–CuI, and AQBr–AE–[Cu(CH3CN)4]ClO4. In the condensation system with a copper(I) catalyst, the Cu(I) species was oxidized to the Cu(II) species by means of an electron transfer from Cu(I) to haloanthraquinone as the reaction proceeded. By adding copper(II) bromide, the induction period vanished in the reaction system of AQBr–AE–CuBr. The copper(II) species increased the catalytic activity of the copper(I) species. The formation of the copper(II) species was responsible for the presence of an induction period and played an important role in the Ullmann condensation reaction of haloanthraquinones with amines in the presence of copper(I) salt as a catalyst.
Excited-State Dipole Moments of Picrates of Pyridine, 2-Methylpyridine, 3-Methylpyridine, and 4-Methylpyridine
Authors: Sedoyama Osamu , Higashi Miwako , Akimoto Yoshinori , Yamaguchi Hiroyuki
Published: July 2006

Measurements of the excited-state dipole moments for picrates of pyridine and methylpyridines have been carried out by spectrophotometry. The contribution of the dative structure Ψ(D+A−) in the excited state of these picrates is larger than the contribution of Ψ(D+A−) in the ground state.
Studies of Heterocyclic Compouds. XII. Structures of Acetylated Products of 5-Hydroxy-4-(2-hydroxyethyl)-3-methylpyrazole
Authors: Ochi Hisao , Miyasaka Tadashi , Arakawa Kiichi
Published: July 2006

Acetylation of 5-hydroxy-4-(2-hydroxyethyl)-3-methylpyrazole (1) produced five acetyl derivatives: 4-(2-acetoxyethyl)-5-hydroxy-3-methylpyrazole (2), 4-(2-acetoxyethyl)-2-acetyl-5-hydroxy-3-methylpyrazole (3), 4-(2-acetoxyethyl)-1-acetyl-5-hydroxy-3-methylpyrazole (4), 5-acetoxy-4-(2-acetoxyethyl)-2-acetyl-3-methylpyrazole (5), and 1-acetyl-5-hydroxy-4-(2-hydroxyethyl)-3-methylpyrazole (6). The partial hydrolysis of 3 and 5 in aq acetic acid gave the monoacetate (2). The triacetate (5) afforded 3 by heating in a mixture of pyridine and meththanol. Migration of the acetyl group from the N1-position to the C5-O- and to the side chain-O-position is suggested. It is also suggested that the triacetate (5) may be effective for acetylation of amines.
The Photocyclization of 3,3′-Diphenyl-2,2′-bi-1H-indene-1,1′-dione
Authors: Toda Fumio , Todo Yozo
Published: July 2006

The photocyclization of the title compound afforded 14-hydroxy-4b-phenylbenz[c]indeno[2,1-a]fluoren-13-(4bH)-one, which is easily isomerized to 4b,13b-dihydro-4b-phenylbenz[c]indeno[2,1-a]fluorene-13,14-dione. The hydrogenation of both compounds gave anti-4b,8b,13a,13b-tetrahydro-4b-phenylbenz[c]indeno[2,1-a]fluorene-13,14-dione.
The Synthesis and Properties of Diacyl Selenides
Authors: Ishihara Hideharu , Sato Shigeyuki , Hirabayashi Yoshio
Published: July 2006

Diacyl selenides were synthesized in good yields by the deselenization of diacyl diselenides, which have conveniently been prepared from acyl chlorides and sodium hydroselenide. The reaction of dibenzoyl selenide with piperidine at 0 °C formed a fairly stable piperidinium salt. The methanolysis of distearoyl selenide gave selenostearic acid as an unstable intermediate.
Nuclear Magnetic Resonance Study of Exchanging Systems. IX. The Slow Rotation of the Methyl Group in Sterically Overcrowded Compounds
Authors: Nakanishi Hiroshi , Yamamoto Osamu
Published: July 2006

In order to obtain information about the slow rotation of methyl groups, the 1H NMR spectra of 9-t-butylethenoanthracene and 9-t-butyltriptycene derivatives were measured at very low temperatures. It was found that the signals of the two methyls of the t-butyl group in these compounds show a considerable line broadening at low temperatures, and it was made clear that the rotation of the methyl groups in these compounds is strongly restricted.
Chemical Transformation of Seldomycin 5 into 3′-Episeldomycin 5 and Its Antibacterial Activity
Authors: Matsushima Hideo , Kitaura Kozo , Mori Yasuki
Published: July 2006

3′-Episeldomycin 5 (7) was synthesized from seldomycin 5. Reaction of hexa-N-ethoxycarbonylseldomycin 5 (2) with o-nitrobenzenesulfonyl chloride gave penta-N-ethoxycarbonylseldomycin 5-2′,3′-epicyclic carbamate (3) in one step. Hexa-N-ethoxycarbonyl-3′-O-tosylseldomycin 5 or hexa-N-ethoxycarbonyl-3′-O-mesylseldomycin 5, prepared from 2, was also converted into 3 by being heated in weakly basic solvents such as N,N-dimethylformamide or pyridine. Compound 3 was hydrolyzed to give 7. Structure of 7 was confirmed by PMR, CMR, MS, and Δ[M] values. Compound 7 was found to be active against resistant bacteria which carry 3′-O-phosphorylating enzymes. Δ[M] values for vicinal amino groups were shortly discussed.
The C–Se Stretching Vibrations and Molecular Conformations of Dialkyl Selenides
Authors: Ohno Keiichi , Hirokawa Takeshi , Aono Seiro , Murata Hiromu
Published: July 2006

The Raman spectra of dialkyl selenides were measured in the liquid and solid states. The most intense Raman lines observed in the 500–700 cm−1 region were assigned to the C–Se stretching vibrations. Correlations of the C–Se stretching frequencies to the molecular conformations were found.
The Separation of Aluminium(III) and Chromium(III) as Their AcAc(acetylacetone)-Complexes, and of Cobalt(II), Copper(II), Magnesium(II), Manganese(II), Nickel(II), and Lead(II) as Their TTA(thenoyltrifluoroacetone)-Complexes, by Extraction Chromatography
Authors: Honjo Takaharu , Honda Yoshio , Matsumoto Tetsu , Honda Ryumon , Kiba Toshiyasu
Published: July 2006

The liquid-liquid extraction behavior of the Al(III) and Cr(III)–AcAc(acetylacetone)–CHCl3 system and of the Mg(II), Pb(II), Mn(II), Co(II), Ni(II), and Cu(II)–TTA(thenoyltrifluoroacetone)–MIBK (isobutyl methyl ketone) system have been studied, and the results have been applied to the separation of these metals as their AcAc and TTA-complexes by extraction chromatography.
Studies of Nitrogen-Phosphorus Compounds. XXVIII. The Thermal Decomposition and Fireproofing Effect of Trimeric and Tetrameric Phosphorus Diamide Nitride
Authors: Kobayashi Etsuro , Kanayama Tadao
Published: July 2006

The thermal decomposition of N3P3(NH2)6·H2O and N4P4(NH2)8·H2O and their fireproofing effects for cellulose have been investigated by means of DTA and TG. These compounds dehydrated at 113 and 124 °C and deammonated at 265 and 271 °C. The activation energies of the dehydration and deammonation were 27 and 42 kcal/mol in the trimer, and 37 and 40 kcal/mol in the tetramer. The cellulose impregnated with either of these compounds flamed up at lower temperatures than did the pure cellulose, but its carbonized product remakably resisted combustion.
Convenient Synthesis of α-Mercaptoalkanoic Acid Esters Using S-Cyanomethyl Thiocarbamates
Authors: Masuyama Yoshiro , Ueno Yoshio , Okawara Makoto
Published: July 2006

The reaction of cyanomethyl dithiocarbamate and S-cyanomethyl thiocarbamate with alkyl halides in aqueous medium selectively gave mono- and di-alkylated products. The treatment of the alkylated products with coned sulfuric acid gave α-mercaptoalkanoic acid esters.
A Phenomenological Description of Electron Paramagnetic Double-Resonance Relaxation of Organic Free Radicals in Solution. I. Theory of ENDOR Based on the Spin-Population Number Method
Authors: Shikata Hideo
Published: July 2006

ENDOR enhancement is phenomenologically described, applying the method of Lloyde and Pake. Emphasis is placed on the effect of incomplete hf separation. It is shown that fractional ENDOR enhancement can approximately be expressed as the product of that which Freed has formulated when the effect is absent, and an modified Allendoerfer-Maki type correlation, T2e2Δω2⁄(c+T2e2Δω2), where c is a constant dependent on the microwave power. Also, a simplified method is proposed for calculating the fractional ENDOR enhancement for a multilevel system consisting of several sets of equivalent protons, when Wn<<We, and it is proven that the week rf power irradiated leads to an ENDOR enhancement proportional to the number of equivalent protons, in the absence of the effect of incomplete hf separation.
Electronic Absorption Spectra of Pyrene and Hydropyrenes
Authors: Yoshinaga Tetsutaro , Hiratsuka Hiroshi , Tanizaki Yoshie
Published: July 2006

Vibronic π-π* transition bands of pyrene, 4,5-dihydropyrene (DHP), and 4,5,9,10-tetrahydropyrene (THP) were assigned by means of dichroism analysis using stretched poly(vinyl alcohol) films. The absorption spectra of the samples in the non-stretched films were divided into two component spectra polarized along the long (x) and short (z) axes of the molecular plane. For pyrene, in addition to the four conventionally-assigned band systems (1Lb, 1La, 1Bb, and 1Ba), some forbidden bands were found in the respective band regions. Most of the vibronic DHP and THP bands were also reasonably well assigned from comparisons with the calculated results for phenanthrene and biphenyl, respectively.
The Effect of Temperature on the Mass Spectra of 1-Alkenes. II
Authors: Hoshino Hiroko , Tajima Susumu , Isogai Fusako , Tsuchiya Toshikazu
Published: July 2006

The mass spectra of 1-alkenes ranging from C5 to C10 were measured at temperatures of the ion source 120–250 °C. Fragmentation M+\oversetm28→(M–28)+ and M+\oversetm28→(M–29)+, where m28 and m29 denote the metastable peaks of the fragmentations, were studied. The behavior of the curve of the intensity ratios R′28=m28⁄F28 and R′29=m29⁄F29(F28 and F29 denote the intensities of the (M–28)+ ion and the (M–29)+ ions, respectively), versus temperature T of the ion source of the mass spectrometer is explained by the quasi-equilibrium theory (QET).