bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxidation of (CD3)2\dotCX Radicals. II. Reaction of (CD3)2CHCl and (CD3)2\dotCCl Radicals with Atomic Oxygen
Authors: Washida Nobuaki , Hatakeyama Shiro
Published: July 2006

The reaction of oxygen atoms with (CD3)2CHCl in a fast flow system was studied with a photoionization mass spectrometer. The (CD3)2\dotCCl radical formed by the initial hydrogen abstraction at the 2-position was detected directly.

(CD3)2CHCl+O(3P)→(CD3)2\dotCCl+OH (1)

The rate data for Reaction 1 were fitted by an Arrhenius expression: k1=(3.5−0.9+1.2)×10−11exp[(−4973±278 cal mol−1)/RT] cm3 molecule−1 s−1 (399–628 K). Among the products formed in the subsequent reaction of (CD3)2\dotCCl radicals with atomic oxygen, CD3CCl=CD2 (31%) produced by the deuterium abstraction and (CD3)2CO (24%) by the oxygen addition were observed. Competition experiments show that (CD3)2\dotCCl radicals react (0.0079±0.0010) times as fast with O2 as with O(3P). In the presence of an excess of O2, CD3CCl=CD2 was observed in decreased yield (3.5%) and (CD3)2CO increased to 56%.
Oxidation of (CD3)2\dotCX Radicals. III. Reaction of 2-Propanol and (CD3)2\dotC(OH) Radicals with Atomic Oxygen
Authors: Washida Nobuaki
Published: July 2006

The reaction of oxygen atoms with 2-propanol was studied in a fast flow system coupled with a photoionization mass spectrometer. Radicals formed in the primary attack of O(3P) atoms on 2-propanol were photoionized by the Xe lamp and identified as the (CH3)2\dotC(OH) radical from (CH3)2CH(OH) and (CH3)2CD(OH) and the (CD3)2\dotC(OH) radical from (CD3)2CH(OH). The major primary product in the subsequent reaction of O+(CD3)2\dotC(OH) was found to be acetone, (CD3)2CO, (62±4%). Formation of 1-propen-2-ol, CD3C(OH)=CD2, by deuterium abstraction and acetic acid, CD3COOH, by oxygen addition were observed in the reaction of O+(CD3)2\dotC(OH). In the reaction of 18O+(CD3)2\dotC(OH), the acetone produced was mostly (CD3)2CO. This fact shows that acetone is produced predominantly by the hydrogen abstraction by O(3P) from the O–H in the (CD3)2\dotC(OH) radical. A part of the acetone is produced also by the addition of O(3P) to the (CD3)2\dotC(OH) radical; i.e., a small but significant signal of (CD3)2C18O was observed in the reaction of 18O+(CD3)2\dotC(OH). The competition experiment between O(3P) and O2 for the (CD3)2\dotC(OH) radical shows that (CD3)2\dotC(OH) react (0.16±0.02) times as fast with O2 as with O(3P). This result suggests that the reaction of (CD3)2\dotC(OH) with O2 is very rapid. It is proposed that the rapid reaction is hydrogen abstraction by O2 from the O–H in the (CD3)2\dotC(OH) radical to form acetone and HO2.
The Crystal Structure of 9-Ethyl-8-hydroxyguanine
Authors: Kasai Hiroshi , Nishimura Susumu , Toriumi Yoshiharu , Itai Akiko , Iitaka Yoichi
Published: July 2006

Analysis of the crystal structure of 9-ethyl-8-hydroxyguanine using X-ray diffraction showed that it is in C-8 keto form. As compared with 9-ethylguanine, significant differences were observed in bond lengths and bond angles of the imidazole ring.
The Synthesis of 12-Ethoxy-4,9-methanoaza[12]annulene, a 12π-Electron Vinylogue of Pyridine
Authors: Ojima J\={u}ro , Masumoto Masayuki , Kuroda Shigeyasu , Hirooka Shuji , Nozawa Yoshihiko
Published: July 2006

The title aza[12]annulene has been synthesized by Beckmann rearrangement of the oxime from the methano[11]annulenone, followed by alkylation of the resulting lactam. Examination of the 1H NMR spectrum indicates that the aza[12]annulene is slightly paratropic.
Effect of 1-Methoxy-5-methylphenazinium Methyl Sulfate on Photocurrent Produced by Rhodospirillum rubrum Chromatophores
Authors: Erabi Tatsuo , Matsumoto Kiyoharu , Itoh Hideki , Takahashi Noritaka , Nishimura Kumiko , Wada Masanori
Published: July 2006

A cathodic photocurrent produced by chromatophores was measured in the presence of 1-methoxy-5-methylphenazinium methyl sulfate (methoxy-PMS). The magnitude of the photocurrent was a function of the wavelength of the incident light, and the photocurrent action spectrum was in agreement with the absorption spectrum of chromatophores. The photocurrent also depended on the concentration of methoxy-PMS or of chromatophores.
Effect of Post-Treatments on the Stability of the Langmuir–Blodgett Film of Fatty Acid Salt in Vacuum
Authors: Iwahashi Makio , Yamaguchi Yoshimi , Kobayashi Koichi , Seimiya Tsutomu
Published: July 2006

The effects of the following treatments on the stability of the Langmuir–Blodgett (L/B) film of fatty acid salt in vacuo have been investigated by radiotracer method: (I) Skeletonization of the L/B film. (II) Transformation of the fatty acid molecules remaining in the L/B film into its soap molecules. (Ill) Perfect formation and deposition of the metal soap monolayer.
Synthetic Photochemistry. XXXIX. Sensitized-Photooxygenation of 2-Benzyltropone, 2-[Hydroxy(4-nitrophenyl)methyl]tropone, and 2-(1-Hydroxy-2-oxo-2-phenylethyl)tropone. A Quenching Effect of Hydroxyl Group in the Vicinity of the Reaction Site
Authors: Mori Akira , Suizu Hiroshi , Takeshita Hitoshi
Published: July 2006

Singlet-oxygen oxidation of 2-[hydroxy(4-nitrophenyl)methyl]tropone gave 6,7-dioxabicyclo[3.2.2]nona-3,8-dien-2-one derivatives in good yields. A change of regioselectivity of the oxygenation with a remarkable rate of enhancement (23 times) in deuteriomethanol vs. methanol could be best explained in terms of the quenching of singlet oxygen by the free hydroxyl group in the vicinity of the reaction site. Similarly studied were 2-(1-hydroxy-2-oxo-2-phenylethyl)tropone and 2-benzyltropone. The stereochemistry of the oxygen adducts was elucidated by a 1H NMR chemical-shift comparison.
1H,1H-Perfluoroalkylation of Enol Silyl Ethers with (1H,1H-Perfluoroalkyl)phenyliodonium Triflates. A New Method for the Preparation of β- and δ-Trifluoromethyl Carbonyl Compounds and Their Higher Perfluoroalkyl Homologues
Authors: Umemoto Teruo , Gotoh Yoshihiko
Published: July 2006

The reaction of enol trimethylsilyl ethers of carbonyl compounds with (1H,1H-perfluoroalkyl)phenyliodonium triflates was promoted successfully by potassium fluoride in dichloromethane at room temperature, giving β-perfluoroalkyl (Rf; CF3, C2F5, i-C3F7, n-C7F15) carbonyl compounds in good yields. An enol silyl ether of an α,β-unsaturated carbonyl compound gave a δ-Rf-α,β-unsaturated carbonyl compound selectively.
Interactions between a Synthetic Phospholipid Vesicle and Cationic Surfactants
Authors: Takasaki Mitsuhiro , Takisawa Noboru , Shirahama Keishiro
Published: July 2006

The interaction between a synthetic phospholipid derivative, the 1,3-ditetradecyl-rac-glycerophosphatidylcholine (2C14–Gly–PC) vesicle, and two cationic surfactants, N-tetradecylpyridinium bromide (TDPBr) and N-tetradecyltrimethylammonium bromide (TDTMABr), were investigated in the hope of obtaining a better understanding of the mechanism of the growth of the vesicle size by the “surfactant-removal” method. The binding isotherms of these surfactants to the lipid vesicle obtained by the surfactant selective electrode were characterized by two-step binding processes; the Langmuir adsorption mechanism in the initial binding, followed by a markedly positive cooperative process. The variation in the hydrodynamic radius, as measured by quasi-elastic light scattering, and the quenching kinetics of pyrene fluorescence with the TDPBr surfactant solution as measured by a stopped-flow method, share a tendency with the binding behavior. The van’t Hoff plots of the initial binding data give a slightly negative enthalpy change, ΔH°, for TDPBr and a relatively large positive ΔH° for TDTMABr. The microenvironmental polarity around pyrene in the molecular assemblies was assessed by means of fluorescence spectroscopy.
The Phase Transition of 1-Alkyl-4-aza-1-azoniabicyclo[2.2.2]octane Bromides, Cn-DABCO-Br (11≤n≤22)
Authors: Imamura Kengo , Nogami Takashi , Shirota Yasuhiko , Ishioka Tsutomu , Kobayashi Masamichi
Published: July 2006

The phase transitions of a series of 1-alkyl-4-aza-1-azoniabicyclo[2.2.2]octane bromides were studied on the basis of DSC, measurements of the ionic conductivities of the bromide anion, and Raman spectroscopy. Two endothermic signals were observed at the temperatures of Tc1 and Tc2(Tc1<Tc2) for most of the materials. The transition enthalpies and transition entropies were not very different for the transitions at Tc1, irrespective of the alkyl-chain lengths attached to DABCO nitrogens. On the other hand, these values tended to increase with an increase in the alkyl-chain lengths for the transitions at Tc2. The temperature dependences of the ionic conductivities of the bromide anion showed abrupt increases in the conductivities by a factor of 2–10. The conductivity jumps were observed around Tc2. The temperature dependences of the Raman spectra gave detailed information on the phase transition; (1) the change in the subcell structure took place at Tc1, with the concomitant occurrence of a conformational change in the alkyl group; (2) above Tc2, the alkyl chain takes a liquid-like disordered form, and a rotational motion of the DABCO portion sets in.
Orientation-Dependent 1H and 13C Isotropic Shifts of Low-Spin Tetracyano(1,2-diamine)ferrates(III)
Authors: Kuroda Yoshitaka , Goto Masafumi , Sakai Tomoya
Published: July 2006

Paramagnetic 1H and 13C NMR signals of low-spin tetracyanodiamineferrates(III), [FeIII(CN)4(diamine)]−, containing ethylenediamine, (R)-1,2-propanediamine, (1R,2R)-trans-cyclohexanediamine, and N,N′-dimethylethylenediamine, were assigned by the use of rapid electron exchange between the FeIII complex and the diamagnetic FeII complex with an identical set of ligands. The C–H on the five-membered chelate ring showed isotropic shifts with different signs depending on their orientations: 14–18 ppm downfield and ca. 16–23 ppm upfield for axial and equatorial protons respectively. The isotropic shifts for the 13C nuclei were attenuated, their signs alternating with each separation by one carbon-carbon bond from the metal ion. The isotropic shift is compared with that of the NiII complex qualitatively in terms of the dipolar and Fermi contact shifts.
The Condensation and Decomposition of Alkaline Earth and Phenyl Phosphoramidates with Acids
Authors: Sato Shoji , Takayanagi Takao , Watanabe Makoto
Published: July 2006

Alkaline earth and phenyl phosphoramidates were reacted with dried hydrogen chloride, acetic acid, and oxalic acid. The alkaline earth phosphoramidates other than the magnesium salt reacted with the acids to produce ortho- and polyphosphates, but did not react with them to make polyphosphates containing imino groups. The hydrolysis of the phosphoramidates to orthophosphate has been considered to be the initiation of the production of polyphosphates:

(Remark: Graphics omitted.)

where M stands for an alkaline earth metal ion. The formation of polyphosphates can be explained, for example, by this equation:

(Remark: Graphics omitted.)

where HA stands for acid. Magnesium phosphoramidate reacted with acetic acid and oxalic acid to produce orthophosphate, polyphosphates, and imidodiphosphate. The production of the imidodiphosphate can be indicated by the following equation:

(Remark: Graphics omitted.)
Studies on Mixed Chelates. XV. An ESR Investigation of Solvatochromic Copper(II) Complexes with Various N-Alkylated Ethylenediamines and β-Diketonates
Authors: Hoshino Naomi , Kodama Naoko , Fukuda Yutaka , Sone Kozo
Published: July 2006

ESR spectra were obtained for frozen solutions of copper(II) mixed chelate complexes, [Cu(diam)(dike)]ClO4, having various N-alkylated ethylenediamines (diam) and β-diketonate ligands (dike). The ESR g-factor (g⁄⁄) determined from apparently axial signals may be correlated by a decreasing function to pKa of dikeH or diam ligand for the series of [Cu(tmen)(dike)]+ or [Cu(diam)(acac)]+, respectively. On the other hand, the g⁄⁄ values gradually increased when the former series of complexes were dissolved in more strongly coordinating solvents, and a relationship was found between g⁄⁄ and Donor Number of the solvent. These trends are regarded as ligand substituent effect and solvent effect on the g⁄⁄ factor, and are analyzed using a crystal field model of a C2v symmetry.
The Base-Catalyzed Isomerization of the Bis(ethylenediamine-N-acetato)cobalt(III) Complex
Authors: Kawaguchi Hiroshi , Niiyama Ryuichi , Ama Tomoharu , Yasui Takaji
Published: July 2006

The isomerization reaction among six geometrical isomers of [Co(edma)2]+, which were all resolved into optically active isomers except for the achiral Ci-trans(O) isomer, has been studied in a basic aqueous solution. It has been found that the reaction is stereoselective and that the main reaction schemes may be described as follows: (1) ΛΔΛ(S,S)-C2-trans(O) \ightleftharpoons ΔΛΔ (R*,S)-C1-cis(O)\ightleftharpoons ΔΛ(R,R)-cis(O)trans(NH) \ightleftharpoons meso(R,S)-Ci-trans(O)→ΛΔΛ(R,R)[or ΔΛΔ(S,S)]-cis(O)trans(NH2) and (2) meso(R,S)-Ci-trans(O)←(+)504CD-mer→ΛΔΛ(S,S)-C2-trans(O). In each of the isomerization steps of (1), the inversion occurs at one of two secondary-N centers of the coordinated edma ligands. The rate of deuteration at the secondary-NH was also measured for all geometrical isomers; a linear relationship between the rates of the deuteration and isomerization was found. It was suggested that the isomerization of the [Co(edma)2]+ system proceeded through the deprotonated five-coordinated intermediates formed by Co–O bond-rupture in the conjugate-base forms.
Kinetic Study of the Polymerization of Styrene in the Presence of Various Organic Hydroperoxides
Authors: Komai Takeshi , Matsuyama Kazuo
Published: July 2006

The polymerizations of styrene initiated by 2,2′-azobisisobutyronitrile have been carried out in the presence of various organic hydroperoxides, such as 1,1-dimethylethyl (Ia), 1,1-dimethylbutyl (Ib), and 1-methyl-1-phenyl-ethyl hydroperoxides (Ic) at 60 °C. The polymerization rate increased with the concentration of Ic, but became rather retarded with that of Ia and Ib. This phenomenon can be explained by the difference in the radical induced decomposition for the hydroperoxides. The hydroperoxide (Ic) decomposes with a radical displacement on the peroxide bond; however, Ia, and Ib, in addition to this reaction, decompose with the radical hydrogen abstraction of the hydroperoxyl group. The peroxyl radical formed (ROO·) subsequently gave rise to a primary radical termination.
Racemic Structure and Optical Resolution by Preferential Crystallization of Dl-Cysteine Salts of Substituted Benzenesulfonic Acids
Authors: Shiraiwa Tadashi , Tazoh Hirohide , Sunami Michio , Sado Yujin , Kurokawa Hidemoto
Published: July 2006

Infrared absorption spectrum, solubility, and thermodynamic analysis indicated that Dl-cysteine salts of benzenesulfonic acid (Dl-BA salt) and 4-ethylbenzenesulfonic acid (Dl-4-EB salt) are conglomerates at room temperature, but Dl-BA salt forms a racemic compound at the melting point. These Dl-salts were optically resolved by the preferential crystallization. As for Dl-4-EB salt, suitable conditions were estimated by the free energy of critical nucleation in supersaturated solutions. The successive preferential crystallization in ethanol at 20 °C was found to give D- and l-4-EB salts with optical purity of 97–100% in the resolution yield of 83–90%. Purification and following treatment with triethylamine gave optically pure D- and l-Cys’s.
Synthetic Studies of Amphotericin B. II. A Facile Synthesis of the C-1–C-12 Segments of the Amphotericin B Aglycon
Authors: Kinoshita Mitsuhiro , Morioka Masahiko , Taniguchi Masato , Shimizu Jun
Published: July 2006

3-Deoxy-1,2-O-isopropylidene-α-d-glycero-d-erythro-pentofuranose (11) was stereoselectively converted into the Witting salt 8 corresponding to the C-1–C-6 portion of amphotericin B aglycon (1) in 57% overall yield in 8 steps. The aldehydic segment 9 or 10 corresponding to the C-7–C-12 portion of 1 was also derived in 6 steps from 11 in 53 or 38% overall yield, respectively. Wittig condensation of 8 with 9 or 10 followed by four-step conversion afforded the C-1–C-12 segment, (3S,5R,8R,9R,11S)-1-O-t-butyldimethylsilyl-12-iodo-3,5:8,9-di-O-isopropylidene-11-O-[(2-methoxyethoxy)methyl]-1,3,5,8,9,11-dodecanehexol(4)or(2S,4R,5R,8R,10S)-1,2-anhydro-12-O-t-butyldimethylsilyl-4,5:8,10-di-O-isopropylidene-1,2,4,5,8,10,12-dodecaneheptol (5) in 26 or 15% overall yield from 11, respectively.
Horner–Emmons Olefination of 4-Hydroxy-2-oxoalkylphosphonates and Related Compounds: Applications to the Syntheses of (±)-Gingerol, (±)-Yashabushiketol, and (±)-Dihydroyashabushiketol
Authors: Tsuge Otohiko , Kanemasa Shuji , Nakagawa Norihiko , Suga Hiroyuki
Published: July 2006

Horner–Emmons olefination of 4-hydroxy-2-oxoalkylphosphonates, readily available by hydrogenation of 5-substituted 3-phosphinylmethyl-2-isoxazolines, gives mainly E-isomers of 1-hydroxy-4-alken-3-ones bearing a variety of substituents at the 1-position. Use of the combination of triethylamine (or DBU)+lithium bromide as a weak base on the O-unprotected phosphonates is favored. Similar olefinations on the isoxazolines, 2-oxo-3-alkenylphosphonates, and 4-alkoxy-2-oxoalkylphosphonates have been also examined. Their synthetic applications to (±)-Gingerol, (±)-Yashabushiketol, and (±)-Dihydroyashabushiketol are described.
Mechanism of the Pyrene-Sensitized Photolysis of N-(1-Naphthoyl)-O-(p-toluoyl)-N-phenylhydroxylainine
Authors: Sakurai Tadamitsu , Inomata Kensuke , Ishikawa Takayoshi , Inoue Hiroyasu , Hoshi Toshihiko , Okubo Jun
Published: July 2006

The title hydroxylamine (NT) undergoes pyrene-sensitized photodecomposition to give rearrangement and fragmentation products. An analysis of linear Stern–Volmer plots, both for the sensitized photolysis of NT and for the fluorescence quenching of pyrene by NT, indicates the involvement of singlet pyrene in this photolysis. The observation of negligible effects of 1,3-cyclohexadiene and trans-stilbene as a triplet quencher on the reaction provides further supporting evidence for a singlet-pathway mechanism. A comparison of the relative state energies of NT and the sensitizer suggests the existence of a reactive singlet-exciplex intermediate formed between the singlet-state sensitizer and the ground-state NT. The results of solvent and micellar effects on the sensitized photolysis establish that electron transfer in the exciplex predominates in a polar solvent, and that in a nonpolar solvent energy transfer in this exciplex plays a major role in the reaction.
2-Amino-1-methyl-1H-imidazole-4,5-dione: Synthesis and the Dimroth Type Rearrangement to Creatone (2-Methyl-amino-1H-imidazole-4,5-dione)
Authors: Yamamoto Hiroshi , Ohira Chikara , Aso Toshiaki , Pfleiderer Wolfgang
Published: July 2006

Treatment of creatinine with BOC-ON gave 2-t-butoxycarbonylamino-1-methyl-1,5-dihydro-4H-imidazol-4-one, which was oxidized with mercury(II) acetate to the corresponding 1H-imidazole-4,5-dione. Deprotection of the amino group of this dione afforded the title compound 4, which in turn was shown to undergo a facile, Dimroth-type rearrangement under weakly acidic conditions to give creatone, thus proving 4 to be the key intermediate in the formation of creatone from various starting materials. The equilibria among these compounds are discussed.
The Study on Peptide and Protein Syntheses. Infrared Spectroscopic Conformational Analysis of Oligo-l-leucines Containing Only One d-Amino Acid Residue
Authors: Narita Mitsuaki , Honda Shinya , Umeyama Hiroshi
Published: July 2006

In order to investigate the influence of a d-amino acid residue on the conformational behavior of peptides and proteins, IR spectroscopic conformational analysis of oligo-l-Leus containing only one d-Ala or d-Val residue was performed in the solid state. For the estimation of their structures, a CPK model and Ramachandran map were very helpful. The d-amino acid residue is clearly inhibited to take the values of the backbone dihedral angles φ and ψ for β-sheet structures formed by l-amino acid residues, while it is allowed for the d-amino acid residue to take the values φ and ψ for helical structures formed by l-amino acid residues. The IR absorption spectroscopic analysis of samples after application of strong shear stress was also useful for the investigation. The effect of shear stress on β-sheet-like structure→helix conformational change is larger for oligo-l-Leus containing a d-Ala residue than those containing a d-Val residue, indicating that the d-Ala residue is more favorable in a helical structure than the d-Val residue. This tendency can be also easily confirmed using CPK model. The significance of this study was discussed in relation to protein synthesis and design of three-dimensional structures of peptides using d-amino acid residues.
Oxidation of Aliphatic Secondary and Benzylic Alcohols to Carbonyl Compounds by Peracetic Acid in the Presence of Sodium Bromide in Acetic Acid
Authors: Morimoto Takashi , Hirano Masao , Ashiya Hiroyuki , Egashira Hidetaka , Zhuang Xiumin
Published: July 2006

Alcohols were smoothly oxidized by peracetic acid in the presence of sodium bromide to give the corresponding carbonyl compounds in good yields.
First ESR Spectrum of a Selenoaminyl Radical
Authors: Miura Yozo , Tsumori Osamu
Published: July 2006

N-(o-Nitrophenylseleno)-3,5-di-t-butylphenylaminyl radical, generated by photolysis of N-(3,5-di-t-butylphenyl)-o-nitrobenzeneselenenamide in the presence of di-t-butyl peroxide, has been studied by ESR spectroscopy. The ESR parameters are compared with those for the corresponding sulfur analogue.
Crystal and Molecular Structure of Bis(benzylamine)bis(thiocyanato)cadmium(II), [Cd(SCN)2(C6H5CH2NH2)2]
Authors: Taniguchi Masahiro , Ouchi Akira
Published: July 2006

The crystal and molecular structure of the title complex was determined by means of a single-crystal X-ray diffraction method. A crystal of CdC16H18N4S2, F. W. 442.8, is monoclinic, with the space group of P21⁄n, a=27.390(19), b=5.7709(8), c=5.8733(9) Å, β=90.35(3)°, U=928.3(7) Å3, Z=2, Dm=1.57(3), Dx=1.58 Mg m−3, and μ(Mo Kα)=1.59 mm−1. The cadmium(II) atom is hexa-coordinated being ligated with two thiocyanato (SCN) sulfur atoms, as well as with two SCN and two benzylamine nitrogen atoms, where the respective pairs of the same kinds of atoms are all in transconfiguration. Each cadmium atom is at the center of symmetry, and the coordination structure around the atom is symmetric. The metal atoms are lined along c-axis, and the pair of the neighboring metal atoms are doubly bridged by SCN ions, although the bridges are a little weaker than the other same type adducts.
The Thermally-Controlled Chemoselective Reduction of 5H-Pyrrolo[3,4-b]pyridine-5,7(6H)-dione with Sodium Borohydride
Authors: Goto Takehiko , Saito Minoru , Sato Ryu
Published: July 2006

The title reaction produced either 2-(hydroxymethyl)nicotinamide or 6,7-dihydro-7-hydroxy-5H-pyrrolo[3,4-b]pyridin-5-one as the major product at room temperature or −20 °C, respectively, along with the corresponding regioisomers as minor products. These novel compounds were converted to known compounds in order to establish their isomeric structures.
Synthesis of Novel Bis-Crown and Double-Armed Crown Ethers Having the 18-Crown-6 Residue
Authors: Naemura Koichiro , Iwasaka Hiroshi , Chikamatsu Hiroaki
Published: July 2006

The 18-crown-6 derivative possessing two hydroxyl groups was prepared from the Diels–Alder adduct of 1,7-(1,2-ethanediylidene)-18-crown-6 with dimethyl 2-butynedioate. By using the crown ether as the key intermediate, novel bis-crown and double-armed crown ethers having the 18-crown-6 residue were synthesized, and their abilities to extract metal picrates were investigated.
Ortho-Selective Alkylation of Phenols with Symmetric Sulfides and Sulfuryl Chloride
Authors: Sato Kikumasa , Inoue Seiichi , Miyamoto Osamu , Ikeda Hiroshi , Ota Tomomi
Published: July 2006

Sulfuryl chloride has been shown to be useful activator for sulfides in the selective preparation of ortho-alkylated phenols via [2,3]sigmatropic rearrangement. By this process, ortho-alkylated phenols have been prepared with various symmetric sulfides in good yields. The rearrangement products having 3-chloropropyl or 3-methyl-3-butenyl moiety have been converted into 2H-1-benzopyran derivatives.
Electroreduction of m-Hydroxybenzoic Arid. Preparation of m-Phenoxybenzyl Alcohol for the New Insecticide Ethofenprox
Authors: Oi Ryu , Shimakawa Chitoshi , Shimokawa Yasushi , Takenaka Shinji
Published: July 2006

The electroreduction of m-hydroxybenzoic acid was examined from both mechanistic and technical points of view, and a practical route to m-phenoxybenzyl alcohol has been developed.
AlBr3 Group Reorientation in NaAl2Br7 and KAl2Br7 Studied by Means of 81Br, 27Al NQR and 27Al NMR
Authors: Yamada Koji , Okuda Tsutomu , Ichiba Sumio
Published: July 2006

81Br NQR spin-lattice relaxation times for MAl2Br7 (M=Na and K) were measured from 77 to 373 K and the reorientational activation energies of the AlBr3 groups about Al–Br(bridge) axes were determined. In the case of NaAl2Br7, the reorientation of the AlBr3 group was also confirmed by a motional narrowing effect of the 27Al NMR using a single crystal. In order to examine the effect of the reorientation on the Al site, 27Al NQR frequencies in NaAl2Br7 were observed as a function of temperature by a SEDOR technique. The asymmetry parameter (η) of the electric field gradient (efg) tensor was found to increase at one of the two Al sites with the onset of the reorientation.
The Influence of Molecular Conformation on the Electronic Relaxation Processes. Complex Formation in the Ground State and Triple Fluorescences of 6-Acetoxyspiro[aceanthyrylene- 2(1H),9′(10′H)-anthracene]-10′-one
Authors: Fujii Tsuneo , Hirano Masahiro , Uno Yoshihiro , Suzuki Satoshi , Hirakawa Kiyoichi
Published: July 2006

The absorption spectra of 6-acetoxyspiro[aceanthyrylene-2(1H),9′(10′H)-anthracene]-10′-one(2) in cyclohexane, dichloromethane, and chloroform have been observed. The absorption spectra have been also observed as a function of concentration of chlorinated methanes in mixtures with cyclohexane. It was revealed that 2 forms a ground state complex with chlorinated methanes. The equilibrium constants for the ground-state complex formation with dichloromethane and chloroform were determined to be 0.14 and 0.17 mol−1 dm3, respectively. The fluorescence and fluorescence excitation spectra of 2 have been obtained as a function of excitation wavelengths and emission wavelengths in cyclohexane and chlorinated methanes. The spiro compound emits structured fluorescence(FM) in cyclohexane. On the other hand, three types of fluorescence bands (FM, FC, and FE) were observed in chlorinated methanes. The FC and FE bands are both structureless and their peak wavenumbers are 20800 and 18700 cm−1. The quenching of fluorescence quantum yield and lifetime were treated by Stern–Volmer kinetics considering the complex formation in both the ground and the excited states of the system. Based on the experimental findings, the origins of FM, FC, and FE bands are explained by the complex formation between 2 and chlorinated methanes in the ground state and exciplex formation in the excited state.
Shock Tube Studies of the Oxidation of Acetylene in Fuel-Rich Mixtures
Authors: Koike Tohru , Morinaga Kihei
Published: July 2006

The oxidation of C2H2 in fuel-rich mixtures was studied in the temperature range 1600–2500 K by a shock-tube technique combined with UV absorption spectroscopy. The absorption profile, attributed to both an increase of C4H2 and a decrease of C2H2, could be modeled with a reaction mechanism comprising 38 elementary reactions. The progress of the oxidation was found to be greatly influenced by the pyrolysis steps of C2H2.
A High-Resolution Solid-State 13C NMR Study of the Secondary Structure of Branched (1→3)-β-d-Glucans from Fungi: Evidence of Two Kinds of Conformers, Curdlan-Type Single-Helix and Laminaran-Type Triple-Helix Forms, as Manifested from the Conformation-Dependent 13C Chemical Shifts
Authors: Saitô Hazime , Tabeta Ryoko , Yoshioka Yûko , Hara Chihiro , Kiho Tadashi , Ukai Shigeo
Published: July 2006

The high-resolution 13C NMR spectra of a variety of fungal branched (1→3)-β-d-glucans were recorded in a DMSO solution and a lyophilized solid in order to gain an insight into the primary and secondary structures in relation to their gel-forming property. We found that all the five lyophilized branched (1→3)-β-d-glucans examined so far, except lentinan, exhibit the laminaran-type triple-helix form, as established by the close resemblance of the 13C NMR spectra among them. On the contrary, lentinan taking the curdlan-type singlehelix conformation was readily converted to the triple-helix form by lyophilization after having been dissolved in a 8M urea solution (1M=1 mol dm−3) and dialysis against distilled water. This finding should be compared with the similar conformational change of curdlan: the conversion by this procedure was at most 50%; annealing at 150°C, followed by slow cooling, was essential for a complete conversion. This treatment did not induce the reverse conformational change from the triple helix to the single helix. The differential behavior of gelformation between the linear and branched (1→3)-β-d-glucans was explained in terms of the molecular conformations in the solid and gel states.
Mutarotation of α-d-Glucose over Several Al2O3 Catalysts
Authors: Ozawa Sentaro , Nakatani Jiro , Sato Masanori , Ogino Yoshisada
Published: July 2006

The mutarotation of α-d-glucose to β-d-glucose has been studied at 25±0.1 °C using five kinds of alumina as catalysts. Two kinds of alumina with measurable surface basicities have exhibited high catalytic activities while the others with little surface basicities have exhibited low activities. Thus, the surface basic sites have been considered to be responsible for the catalytic activity observed. Any of crystal structures, surface areas, pore structures, and surface elemental compositions have no relation to the catalytic activity. It has also been revealed that the kinetics of the reaction is explained by a surface reaction mechanism

α+1 \undersetKα\ightleftharpoons αad \oversetk1\undersetk2\ightleftharpoons βad \undersetKβ\ightleftharpoons β+1,

where 1, Kα, Kβ, k1 and k2 denote the active site, the adsorption equilibrium constant for α, the adsorption equilibrium constant for β, the rate constant for the surface forward reaction, and the rate constant for the surface backward reaction, respectively, and the subscript ad denotes an adsorbed state. The result of kinetic analysis has revealed that Kβ>Kα, indicating that the adsorption of β-glucose is stronger than that of α-glucose. This also supports the view that the surface basic sites are responsible for the catalytic activity.
Reaction of Allyl Phenyl Ether over Various Liquid Metal Catalysts
Authors: Ozawa Sentaro , Sasaki Yoshiki , Ogino Yoshisada
Published: July 2006

Allyl phenyl ether has been reacted over various kinds of liquid metal catalysts (Sn, Ga, In, Tl, Pb, Cd, Bi, Zn) and without catalysts in the temperature range of 320–500 °C. Phenol (PN), 1,5-hexadiene (HD), benzofuran (BF), and o-allylphenol (o-AP) together with small amounts of unknown compounds have been found in the condensable products. The results of correlation among the conversion for PN, HD, and BF as well as the results of kinetic simulation of the products distribution have revealed that only the o-AP formation is catalyzed by the liquid metal. A clear compensation effect between the frequency factor and the activation energy has been found for the o-AP formation reaction, suggesting that a radicalic high energy and high entropy transition state is involved in the catalysis. A good correlation between the methyl group-catalyst metal bond energy and kinetic parameters of the o-AP formation reaction has also supported the radicalic transition state model.
Interaction between Dodecyltrimethylammonium Chloride and DNA
Authors: Shirahama Keishiro , Takashima Koji , Takisawa Noboru
Published: July 2006

Binding of dodecyltrimethylammonium cation to calf thymus DNA was studied by using the surfactant-selective electrode as a function of added electrolyte concentration at various temperatures. Binding is highly cooperative and biphasic. An abruptly occurring binding attains a slight shoulder within a very narrow equilibrium concentration range followed by a further augmentation in binding, as the equilibrium concentration is increased. Temperature caused relatively small shift in binding isotherm, but a distinct inversion point was found around 27 °C. Above this temperature the isotherm shifts to the left and then to the right below it. Analogous binding studies as above were repeated with heat-denatured DNA, which binds the surfactant with higher intrinsic affinity but less cooperatively than the intact DNA. A fluorescent probe, pyrene, was employed to assess the microenvironmental polarity of pyrene in DNA before and after surfactant binding. The surfactant–DNA complex has a hydrophobic region akin to ordinary micelle.
Molecular Structure of the exo-Diels–Alder-Adduct of 5-Methoxy-2-methyl-4-(p-nitrophenyl)oxazole with N-Methylmaleimide
Authors: Ibata Toshikazu , Toyoda Jiro , Tamura Hatsue , Ogawa Kazuhide
Published: July 2006

The molecular structure of the exo-Diels–Alder adduct of 5-methoxy-2-methyl-4-(p-nitrophenyl)oxazole with N-methylmaleimide was determined by X-ray analysis. The crystals are triclinic, space group P\bar1, with a=9.160(2), b=11.182(2), c=8.816(1) Å, α=92.39(1), β=116.47(1), γ=100.60(1)°, Z=2, Dx=1.455 Mg m−3, Dm=1.458 Mg m−3, μ(Cu Kα)=9.76 cm−1. The configuration of the exo-adduct is consistent with that predicted on the basis of the NMR data.
A Facile Method for the Production of d-p-Hydroxyphenylglycine. Asymmetric Transformation of Dl-p-Hydroxyphenylglycine Using (+)-1-Phenylethanesulfonic Acid
Authors: Yoshioka Ryuzo , Tohyama Masanori , Yamada Shigeki , Ohtsuki Osamu , Chibata Ichiro
Published: July 2006

A practical method for the production of d-p-hydroxyphenylglycine, useful as a starting material for preparing semisynthetic penicillins or cephalosporins, has been developed. The diastereomeric salts of Dl-p-hydroxyphenylglycine with (+)-1-phenylethanesulfonic acid as a resolving agent, were efficiently resolved into less soluble d-p-hydroxyphenylglycine (+)-1-phenylethanesulfonate [d-HPG·(+)-PES] and soluble l-HPG·(+)-PES by the fractional crystallization of its salts in aqueous solution. The soluble l-HPG·(+)-PES could be easily epimerized into Dl-HPG·(+)-PES by heating it with water containing a 0.1 molar equivalent of free Dl-HPG in an autoclave. When the fractional crystallization of Dl-HPG with (+)-PES was simultaneously carried out under the epimerizing conditions, the Dl-HPG·(+)-PES was transformed into d-HPG·(+)-PES in up to 90% yield. The present asymmetric transformation should be a suitable method for preparing d-HPG in a large scale.
Preparation of Polyacetoxytropones and Polyhydroxytropolones by Acetolysis and Hydrolysis of Halotroponoids by Acetyl Trifluoroacetate with Exhaustive Displacement of Halogens on the Tropone Ring. Predominant Formation of Reductive Acetolysates from Fully-Substituted Tropones
Authors: Takeshita Hitoshi , Mori Akira , Kusaba Tomoyuki , Watanabe Hiroyasu
Published: July 2006

Di-, tri-, and tetrahydroxytropolones were prepared in good yields by the acetolysis of corresponding halotropones or polyhalotropolones with acetyl trifluoroacetate followed by acetic acid hydrolysis. However, using the same treatment to obtain hexaacetoxytropone with fully substituted acetoxyhalotropones predominantly yielded fewer substituted acetoxytropones than expected; the mechanism of formation was shown to involve an acetic acid-mediated reduction of intermediary formed acetoxy-p-tropoquinone equivalents. A couple of 2,7-unsubstituted 3,4-diacetoxytropones were deduced to have cyclized 1,3-dioxole structures, 2-acetoxy-2-methyl-5H-cyclohepta-1,3-dioxol-5-ones. An acetolysis of the brominated 5-isopropyltropolones furnished an acetylated by-product, 2,3,7-triacetoxy-5-(1,1-dimethyl-2-oxopropyl)tropone, which might be formed by the acylation of an intermediate, 3,4,5,6-tetraacetoxy-8,8-dimethylheptafulvene.
Convenient Synthesis of Alkanediyl Bis(alkyl trithiocarbonate)s from Alkanedithiols with Alkyl Halides and Carbon Disulfide in the Presence of Phase-Transfer Catalyst
Authors: Sugawara Akira , Hasegawa Ken , Suzuki Ken-ichi , Takahashi Yukio , Sato Ryu
Published: July 2006

Alkanediyl bis(alkyl trithiocarbonate)s were conveniently synthesized by treating alkanedithiols with alkyl halides and carbon disulfide in the presence of a phase-transfer catalyst.
Reactions of Aryl Ketones and Coumarins with Iodine(III) Tris(trifluoroacetate)
Authors: Fukuyama Norihiro , Nishino Hiroshi , Kurosawa Kazu
Published: July 2006

The reaction of acetophenones with iodine(III) tris(trifluoroacetate) yields 3′- and/or 2-iodo derivatives, depending upon the substituent on the aromatic ring and the reaction conditions. The reaction was examined by changing the molar ratio of acetophenone versus the reagent, reaction temperature, and solvent. In similar reactions flavanones and coumarins gave iodo derivatives in which iodine is incorporated at various positions orientated by the oxygen functions. 1,2-Diphenylethanone yields 2-hydroxy-2-(2-iodophenyl)-1-phenylethanone and 1-(2-iodophenyl)-2-phenylethanedione. The reactions of other aromatic ketones such as 9-xanthenone, 9-fluorenone, and anthrone also give iodo derivatives in moderate to good yields. The mechanisms for the iodination at the α-carbon to the carbonyl group have been discussed.
Efficient Carbonyl Addition of Polyfluorochloroethyl, -ethylidene, and -ethenyl Units by Means of 1,1,1-Trichloro-2,2,2-trifluoroethane and Zinc
Authors: Fujita Makoto , Hiyama Tamejiro
Published: July 2006

Thermally stable zinc carbenoid CF3CCl2ZnCl was prepared from 1,1,1-trichloro-2,2,2-trifluoroethane and zinc powder in N,N-dimethylformamide and was allowed to add to carbonyls of aldehydes and α-keto esters in excellent yields to give 1-substituted 2,2-dichloro-3,3,3-trifluoro-1-propanols. Employment of excess zinc induced further reductive β-elimination to afford 1-substituted 2-chloro-3,3,3-trifluoropropenes (3) and 1-substituted 2-chloro-3,3-difluoro-2-propen-1-ols (4). Exclusive formation of 3 was achieved by use of acetic anhydride as the co-reagent, whereas 4 was produced with an aluminium chloride catalyst highly selectively.
Spectral Characteristics of Phenylenediamines and Their Various Protonated Species
Authors: Manoharan R , Dogra Sneh Kumar
Published: July 2006

Increase in the Stokes shift [\barνabs(max)−\barνflu (max)] with an increase in the polarity and hydrogen-bonding capacity of the solvents is the maximum for p-phenylenediamine and the minimum for m-phenylenediamine. These studies have indicated that the two amino groups in o- and p-phenylenediamines are not in the same plane of the benzene ring. Spectral characteristics of monocations and dications resemble to those of aniline and benzene respectively. pKa values for the dication–monocation and monocation–neutral equilibria have been determined, both in S0 and S1 states, and discussed.
Mass Spectral and Pyrolytic Studies of Some 4,4-Disubstituted 1,4-Dihydro-2H-3,1-benzoxazin-2-ones
Authors: Acharya Baman Prasad , Misra Bijaya Kumar , Rao Yerramalli Ramachandra
Published: July 2006

Pyrolysis of 4,4-diaryl-1,4-dihydro-2H-3,1-benzoxazin-2-ones at 230–240 °C gives 9-arylacridines and (2-aminophenyl)diarylmethanes. Their formation correlates well with the mass fragmentation of the respective parent compounds.
Adsorption of Cu2+ or Hg2+ Ion on Resins Prepared by Crosslinking Metal-Complexed Chitosans
Authors: Ohga Kazuya , Kurauchi Yoshiaki , Yanase Hiroshi
Published: July 2006

Crosslinking metal-complexed chitosans (metal ions=Cu(II), Cd(II), Zn(II), Ni(II), and Fe(III)) with (chloromethyl)oxirane yields resins having higher abilities to adsorb Cu2+ than a resin obtained from chitosan in the absence of metal ion. Resins from Cd(II)–chitosan complex can act as effective adsorbents for Hg2+; their Langmuir’s adsorption parameters depend on the quantity of (chloromethyl)oxirane used.
Effect of Catalyst on the Oxygenation of Styrene with BH4− and Molecular Oxygen
Authors: Okamoto Tadashi , Sasaki Yoshihiro , Sasaki Ken , Oka Shinzaburo
Published: July 2006

The effects of equatorial ligands and central metals on the catalytic conversion of styrene to 1-phenylethanol were examined. Accompanying hydrogenation and hydrodimerization of the substrate to ethylbenzene and 2,3-diphenylbutane, respectively, was facilitated in the presence of a catalyst ligated with an electron-releasing ligand such as 1,4,8,11-tetraazacyclotetradecane or sulfurcontaining ligands.
Formation of Chlorosulfonium Salt of 1,5-Dithiacyclooctane and Transannular Sulfur–Sulfur Interaction in Hydrolysis of Its Salt
Authors: Fujihara Hisashi , Akaishi Ryouichi , Furukawa Naomichi
Published: July 2006

The reaction of 1,5-dithiacyclooctane 1-oxide (2) with thionyl chloride afforded the corresponding chlorosulfonium chloride as a stable salt and an evidence for the intermediary formation of the bis-sulfide dication with an equilibrium mixture of the chlorosulfonium salt was found. In contrast to 2, 1,4-dithiacyclohexane 1-oxide (6) reacts with thionyl chloride like a simple sulfoxide.
Terpenoids. X. Natural Autoxidation of Thujopsene
Authors: Nagahama Shizuo , Tazaki Masato
Published: July 2006

The natural autoxidation of thujopsene 1 afforded three dimeric peroxides (14,15, and 16) as the major products. 9α,10-Epoxy-8α-thujopsanol 17 was separated as a minor product besides other known compounds, allylic alcohols 2 and 3, mayurone 7, thujopsane-8α,9α-diol 11, and thujopsan-9-ones 19 and 20.
Low Temperature Synthesis of Dispersed Fine Particle of Cobalt Aluminate—A New Application of Zeolite
Authors: Ohgushi Tatsuo , Umeno Shigeru
Published: July 2006

CoAl2O4, with the spinel structure in a dispersed form, was synthesized at 400 °C by using zeolite A as a starting material. A specific surface area of the products was measured by adsorption of (CH3)2CHCH3 gas at −110 °C and the mean size of the product particles was estimated to be about 14 nm.
Excited-State Reactions of Coumarins in Aqueous Solutions. V. Fluorescence Lifetimes of 7-Ethoxycoumarin in Acidic Solutions
Authors: Moriya Tetsuo
Published: July 2006

The fluorescence lifetime of 7-ethoxycoumarin (7EC) was measured in acidic aqueous solutions while varying the concentration of Cl− as a fluorescence quencher. The subsequent analysis of the two-component fluorescence decay curves indicated that the protonated species in the excited state led to the fluorescence quenching; this result was quantitatively consistent with the fluorescence-yield study under steady-state conditions.
Preparation of Noble Metal Organosols Containing Polyethylene Glycol Mono-p-nonylphenyl Ether
Authors: Nakao Yukimichi , Kaeriyama Kyoji
Published: July 2006

Stable organosols of ruthenium, rhodium, palladium, and platinum were prepared by evaporating the corresponding noble metal hydrosols containing nonionic surfactant, polyethylene glycol mono-p-nonylphenyl ether, followed by dissolving the resulting residues in organic solvents such as chloroform. The organosol of the noble metals was exclusively yielded at a definite range of the surfactant concentration. A mechanism for the formation of the organosols is proposed.
Acridine Derivatives. I. Molecular Structure of the Novel Acridinyl-Substituted Uracil, 5-(9-Acridinyl)-6-amino-1,3-dimethyluracil
Authors: Kimura Michio
Published: July 2006

The reaction of enamine between 9-chloroacridines and 6-aminouracil derivatives give novel acridine substituted uracils, the structures of which have been determined by means of an X-ray analysis of 5-(acridin-9-yl)-6-amino-1,3-dimethyluracil hydrochloride dihydrate, C19H16N4O2·HCl·2H2O. The crystal is triclinic with a space group P\bar1; also, a=8.763(3) b=16.130(9), c=7.620(2) Å, α=117.51(4), β=83.81(3), γ=94.21(4)°, Z=2, V=949.3 Å3, Dc=1.16 g cm−3, and μ=5.30 cm−1 for CuKα. The structure was solved by a direct method and refined by a block-diagonal least-squares procedure: R=0.074 for 2810 reflections with |Fo|>3σ(|Fo|). The crystal is composed of the title compound, chloride anion, and two molecules of water held together by hydrogen bonds (described in Table 4).
Studies on 5-8 Fused Ring Compounds. IV. The Syntheses of 5-8-5 Fused Ring Compounds and the Conformations of Their Eight-Membered Rings
Authors: Umehara Misao , Hishida Shinzaburo , Okumoto Satoshi , Ohba Shigeru , Ito Masatoki , Saito Yoshihiko
Published: July 2006

The isomers, cis-cisoid-cis- and cis-transoid-cis-tricyclo[9.3.0.04,8]tetradecane-2,9-dione (2 and 3) and cis-cisoid-cis-tricyclo[9.3.0.03,7]tetradecane-2,9-dione (4) were synthesized by the photocycloaddition of bicyclo[4.3.0]nonane-2,4-dione (1) to cyclopentene. X-Ray analyses of those compounds revealed that the conformations of the eight-membered rings are twist-boat in 2, chair in 3, and boat–chair form in 4.
X-Ray Structure and Magnetism of μ-Bromo-μ-pyrazolatobis(diethylenetriaminecopper(II)) Perchlorate Monohydrate
Authors: Matsumoto Keiji , Ooi Shun’ichiro , Mori Wasuke , Nakao Yasuo
Published: July 2006

The structure of the title compound has been determined by an X-ray method. The dinuclear complex is composed of two Cu(dien) units which are bridged by pyrazolate and Br− anions. The geometry around each copper(II) may be described as a square pyramid. The antiferromagnetic interaction within the dinuclear complex has been observed (J=−14 cm−1, H=−2JS1·S2).
Some Applications of Thermodynamic Equations on the Pressure Effect of the Chemical Reactions
Authors: Jee Jong-Gi
Published: July 2006

This paper is concerned with the theoretical derivation of the linear relationship between enthalpy and entropy for pressure change in chemical equilibria, and its application to the dissociation equilibria of some 4-substituted 1-methylpyridinium iodides in water–ethanol mixture. The isoequilibrium temperature, \barβ, for this system was derived to be 322 K.
Reduction of Nitrostyrenes to Nitroalkanes with a NADH Grafted Model
Authors: Tréfouel Thierry , Tintillier Patrik , Dupas Georges , Bourguignon Jean , Quéguiner Guy
Published: July 2006

Grafting of the 1,4-dihydronicotinamide structure on a Merrifield type resin is described. With this reagent, arylnitroethanes have been obtained by regioselective reduction of β-nitrostyrenes. The yields are good and no dimeric compounds are formed. The role of magnesium ions in these reductions is different from that observed with classical NADH models.
Molecular Dynamics Simulation of Liquid Water
Authors: Tokiwano Kazuo , Arakawa Kiyoshi
Published: July 2006

A molecular dynamics simulation has been performed for a fluid system containing 1000 water molecules confined to a cubical box at mass density 1 g cm−3, where the ST2 type intermolecular potential has been used. Newtonian equations of motion of molecules were solved according to the method of constraints proposed by Ryckaert et al. Atomic radial distribution functions and corresponding partial structure functions at 24 and 93 °C were given and compared with theoretical calculations for the pentamer–monomer mixture model and neutron diffraction data. The agreement among the three was found to be satisfactory on the whole. In order to investigate how profoundly the periodic boundary condition influences upon the calculated values, the difference between the hydrogen-bonding behavior of molecules near the boundary and that of those in the central part of the box was examined into details. The population of hydrogen bonds near the boundary was found to be about 10% lower than that in the central part including about 210 molecules. In addition to these static properties the self-diffusion process was investigated.