bluuebunny/crossref_metadata_2025 huggingface dataset:
The Magnetic Properties of Manganese(II) Phthalocyanine
Authors: Miyoshi Hirokazu , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo
Published: July 2006

The magnetic transition from the ferro- to the para-magnetic state of manganese(II) phthalocyanine (C32H16N8Mn) has been observed by measurements of the magnetic susceptibility, the magnetization and the proton magnetic resonance in the low-temperature range. The positive Weiss constants were obtained from the static susceptibility measurements and the proton magnetic measurements. Moreover, the magnetic-field dependences of the experimental results were found in the low-temperature range. All of those findings confirm the ferromagnetic behavior of this substance in the lower-temperature region. From the measurements of the frequency shift in the resonant circuit of the proton magnetic resonance apparatus, the transition temperature was determined to be 8.6 K. A possible mechanism of long-range ordering was also discussed on the basis of the crystal structure of this substance.
Ion-selective Electrodes Sensitive to Some Organic Compounds Used as Drugs
Authors: Kina Kenyu , Maekawa Nobuko , Ishibashi Nobuhiko
Published: July 2006

Drug ion-selective electrodes with a liquid membrane have been developed which are sensitive to methacholine, neostigmine, N-1-methyl nicotinamide, diphenhydramine, vitamin B1, vitamin B6, p-aminosalicylic acid (PAS), and salicylic acid. Crystal violet or ferroin-compound cations and dipicrylamine or tetraphenylborate anions were used as the ion-exchange sites in the liquid membrane. Each liquid membrane was prepared by using the solvent-extraction method and exhibited an appropriate Nernstian response to the respective ion down to 10−4 or to 10−5 M. The electrode performances, including the selectivity coefficients, are summarized in Table 1.
Catalytic Function of Metal Chelates in the Hydration of 2-Pyridinecarbonitrile
Authors: Watanabe Ken-ichi , Komiya Shigeo , Suzuki Shinnichiro
Published: July 2006

The catalytic effects of various transition metal complexes on the hydration of 2-pyridinecarbonitrile have been investigated. In these homogeneous catalytic reactions, free 2-pyridinecarboxamide was obtained as the sole reaction product. The transition metal species of the complexes used were Cu(II), Ni(II), Co(II), Co(III), and Pt(IV), while the ligands were ethylenediamine, bipyridine, glycine ion, and 2-pyridinecarboxamide. The complexes of Cu(II), Ni(II), and Co(II) were all catalytically active for the hydration, but those of Co(III) and Pt(IV) were inactive. No reaction occurred with 3- and 4-pyridinecarbonitriles under the same reaction conditions. The effect of the pH was remarkable. The active complex catalysts were classified into three types.
The Reaction of Nitriles under High Pressure. III. The Cyclotrimerization of Aliphatic Nitriles in the Presence of Alcohols and the Rearrangement of the Resulting Trialkyl-1,3,5-triazines to 4-Aminopyrimidines
Authors: Yanagiya Koshin , Yasumoto Masahiko , Kurabayashi Masahiro
Published: July 2006

The examination of the simultaneous formation of symmetrically tri-substituted 1,3,5-triazines, 4-amino-2,5,6-substituted pyrimidines and N-pyrimidylamidines in mixtures of lower alcohol and nitrile with more than two hydrogen atoms on the α-position under pressures of a few thousand atm afforded the following information: (1) the triazine is formed by the cyclo-trimerization of the iminoether which is derived from the nitrile and the alcohol; (2) the pyrimidine is formed by the rearrangement of the previously-formed triazine. This rearrangement is caused by an attack of the nucleophilic iminoether on a carbon atom of the triazine ring; and (3) the amidine is assumed to be formed, together with the pyrimidine, by the same attacking mechanism.
Kinetic and NMR Spectroscopic Studies of the Fusion Reactions of Chloropurines with 1,2,3,5-Tetra-O-acetyl-d-ribofuranoses
Authors: Hosono Akira , Fujii Kiyohisa , Tada Toshizo , Tanaka Hisayuki , Ohgo Yohko , Ishido Yoshiharu , Sato Tetsuo
Published: July 2006

A kinetic study of the fusion reaction and the reaction in dimethyl sulfoxide of 2,6-dichloropurine with 1,2,3,5-tetra-O-acetyl-β-d-ribofuranose was undertaken, and both of them were proved to be of the second order. The activation energy and the activation entropy of the reaction in dimethyl sulfoxide were obtained: Ea=38.0 kcal/ mol and ΔS\eweq=+15.3 cal · mol. The reaction was thus concluded to be bimolecular involving a considerable unimolecular character. Subsequently, the fusion reactions of 2,6-dichloro- and 2,6,8-trichloropurine with 1,2,3,5-tetra-O-acetyl-α- and -β -d-ribofuranose were examined by NMR spectroscopy with respect to the relative content ratios of all the materials and products in each reaction mixture; the results were found to be in good agreement with those obtained by the above kinetic study. On the basis of these results, the mechanism of the fusion reaction was discussed.
Oxidative Additions of Alkyl Halides to Palladium(0) Carbonyl Complex
Authors: Kudo Koji , Sato Michito , Hidai Masanobu , Uchida Yasuzo
Published: July 2006

Oxidative addition reactions of alkyl halides to Pd(CO)(PPh3)3 were studied. Vinyl chloride, allyl chloride, allyl bromide, methallyl chloride, benzyl bromide, methyl iodide, and iodobenzene react with Pd(CO)(PPh3)3 to afford the corresponding acyl complexes of the type to the type trans-PdX(COR)(PPh3)2. The reactions proceed rapidly when the dissociation energy of carbon-halogen bond in the saturated alkyl halides is smaller than about 60 kcal/mol. In the case of the unsaturated alkyl halides the more inert carbon-halogen bond can be activated by initial formation of π complexes.
Crystal and Molecular Structure of ω-Amino Acids, ω-Aminosulfonic Acids and Their Derivatives. VI. The Crystal and Molecular Structure of Dl-γ-Amino-β-hydroxybiityric Acid (GABOB), A Nervous Inhibitory Chemical Transmitter
Authors: Tomita Ken-ichi , Harada Masahiro , Fujiwara Takaji
Published: July 2006

Dl-γ-Amino-β-hydroxybutyric acid (GABOB), C4H9O3N, forms monoclinic plate crystals of space group P21/c, with a=7.43, b=8.29, c=9.34 Å, β=110.9°, and four molecules in the unit cell. Intensity data were collected by a film method. The structure was solved by the direct method with the symbolic addition procedure, and refined by least-squares methods to R=0.096. GABOB molecule having the zwitterionic structure, NH3+–CH2–CH(OH)–CH2–COO^-, forms trans-zigzag skeletal conformation with an intramolecular OH···O hydrogen bond of 2.773 Å, and contacts with each other by three dimensional network of NH···O and OH···O hydrogen bonds.
Polarographic Studies of the Associated Ion-pairs of Polyphosphate with the Hexaamminecobalt(III) Ion
Authors: Matsuura Niro , Umemoto Kisaburo , Takizawa Masao , Sasaki Yukio
Published: July 2006

The polarographic behavior of the hexaamminecobalt(III) ion was studied in solutions of polyphosphate with different numbers of chains. The decrease in the diffusion current, id with an increase in the phosphate (Cp)-to-hexaamminecobalt(III) (CCo) mole ratio was found to be proportional to 1/4 the power of the molecular weight, M, of the Co(NH3)63+-polyphosphate. This fact shows the associated ions between Co(NH3)63+ ions and polyphosphate anions are transported to the electrode by diffusion at a rate depending on the square root of the molecular weight of the diffusion depolarizer. From the shift of the half-wave potential in the presence of excess polyphosphate, the chemical compositions of the associated ion-pairs were determined as a function of log Cp/CCo.
Classification of Polarographic Current-Potential Curves of Inorganic Anions as a Function of Reduction Potentials
Authors: Umezawa Yoshio , Hirota Michio , Fujiwara Shizuo
Published: July 2006

DC polarographic behaviors of a variety of inorganic anions are examined systematically. Irrespective of chemical species, the shapes of current-potential curves are classified into three groups as a function of reduction potentials: i) E1⁄2>0 V(SCE); The so-called minima cannot be observed beyond the ecm potentials, ii) 0 V>E1⁄2>ecm; The minima can be observed, iii) E1⁄2<ecm; The distortion at the rising portion of the DC polarograms can always be observed. These results suggest that whether the minima can be observed or not is due to the difference in the relative position of half-wave potentials with respect to the ecm potential. Furthermore, it is likely that the distortion at the rising portion of the DC polarogram of Group iii) is similar in origin to that of the minima of Group ii). The present results are discussed in terms of the electron density and electronic energy level of electrons in the metal electrode. The discussion based on the phenomenological equation of Butler was also given for the sake of comparison to explain the observed phenomena.
Superacids and Their Derivatives. III. Kinetics of the Oxonium Ion Formation from Superacid Esters and Tetrahydropyran. Oxonium-Ester Equilibria
Authors: Kobayashi Shiro , Ashida Tadashi , Saegusa Takeo
Published: July 2006

Kinetic studies on the oxonium formation reaction between superacid esters (ROSO2X) and tetrahydropyran (THP) were carried out by means of NMR spectroscopy. The reaction was found to be an equilibrium process.

(Remark: Graphics omitted.)

The rate constant (k) of Sn2 reaction and the equilibrium constant (1⁄K=k⁄k′) were determined. The solvent effect was examined and k was found to be in the order: nitrobenzene>chlorobenzene≈CH2Cl2>liquid SO2. The effects of R and X in ROSO2X were studied. Relative reactivities of primary alkyl series in the reaction of ROSO2C1 with THP were: Me: Et: n-Pr=4.63: 1.0: 0.294 in CH2Cl2 and Me: Et: n-Pr=3.19: 1.0: 0.452 in nitrobenzene. The effect of X on k was in the order Cl≈CF3>F, the 1⁄K value being also extremely low when X=F. The result was discussed in relation to the kinetics of the polymerization of tetrahydrofuran (THF) by ROSO2X.
Photochemistry of Heterocyclic Compounds. VI. The Photochemical Behavior of Phenazine in Hydroxylic Solvents
Authors: Wake Shigeo , Otsuji Yoshio , Imoto Eiji
Published: July 2006

The photochemical behavior of phenazine in acidified hydroxylic solvents varied with the concentration of acids present in the solutions. Irradiation of phenazine in an aqueous phosphoric acid afforded a 1 : 1 mixture of phenazinium and 1-hydroxyphenazinium cation radicals which were converted to a mixture of phenazine and 1-hydroxyphenazine. Irradiation in moderately strongly acidified alcohols (0.1–1.0 M HCl in alcohols) or in acetic acid containing 0.1 M p-toluenesulfonic acid yielded a 1 : 1 mixture of phenazine and the corresponding 1-alkoxyphenazines or 1-acetoxyphenazine after work-up of the reaction mixture. On the other hand, irradiation in a very strongly acidified methanol (5.6–9.6 M HCl in methanol) gave only the phenazinium cation radical. Mechanistic studies revealed that in the moderately strongly acidified media the reaction proceeds through a solvent-addition to the excited singlet phenazinium monocation, and in the very strongly acidified methanol the reaction proceeds through an electron transfer from the solvent to the excited singlet phenazinium dication.
The Structure and Reactivity of Organic Ions in Gas-phase Radiolysis. VIII. The C7H7+ Ion from Toluene and Ethylbenzene
Authors: Sagi Nobuo , Yamamoto Yukio , Nagaoka Kenji , Takamuku Setsuo , Sakurai Hiroshi
Published: July 2006

The gas-phase radiolysis of a mixture of toluene or ethylbenzene and dimethylamine has been studied at room temperature as a function of the dimethylamine pressure in order to investigate the structure and reactivity of the C7H7+ ion. The structure of the C7H7+ ion which takes part in the subsequent ion-molecule reaction was suggested to be the benzyl type on the basis of the reaction products. The radiolyses of toluene-α-d3 and ethylbenzene-α-d2 in the presence and in the absence of dimethylamine have been investigated, and the following information has been obtained: (i) the C7H7+ ion formed from toluene and ethylbenzene mainly consists of the benzyl ion, retaining its original structure; (ii) two types of scrambling processes may be involved in the C7H7+ ion formation, one of which, especially important in the case of toluene, includes the ring expansion of the original molecular ion, while the other consists of repeated rapid isomerization between the benzyl ion and the tropylium ion. These results were compared with those of mass spectrometric studies, which indicate that an almost complete isotope scrambling occurs, hence supporting the symmetrical tropylium structure for the C7H7+ ion.
UV-Spectra of Fluorenyl Salts in the Binary Mixtures of DME and Benzene
Authors: Takaya Katsuhiko , Ise Norio
Published: July 2006

The temperature dependence of UV spectra of fluorenyl lithium and sodium was investigated in 30, 40, and 50 vol% dimethoxyethane (DME)–benzene mixtures. The lithium salt had two absorption peaks at 352 and 373 nm, and the sodium salt at 358 and 373 nm. The fraction of solvent-separated ion pairs for the sodium salt was much lower than that of the lithium salt, and the heat of conversion (−ΔHi) of contact-ion pairs to solventseparated ion pairs was larger (9–11 kcal/mol) for the sodium salt than that (1–4 kcal/mol) for the lithium salt.
Inositol Derivatives. 8. Azidolysis of Tri- and Tetra-sulfonates of myo-Inositol
Authors: Suami Tetsuo , Ogawa Seiichiro , Oki Shuichi , Kunitomo Hideo
Published: July 2006

Reactions of the azide ion with four trisulfonates (1,4,5-, 1,4,6-, 1,5,6-, and 4,5,6-) and one tetrasulfonate (1,4,5,6-) of myo-inositol were studied. The structures of the new azido compounds were established by PMR spectroscopy and reaction sequences. The mechanism of neighboring-group participation reactions were discussed.
Kinetic Studies of the Reaction between Sodium Dodecyl Sulfate and Pinacyanol Chloride
Authors: Tatsumoto Nobuhide , Takeda Kunio , Isshiki Shunji , Yasunaga Tatsuya
Published: July 2006

Below the critical micelle concentration, a kinetic study of the aggregate formation reaction of sodium dodecyl sulfate and pinacyanol chloride was made by means of a stopped-flow system combined with a rapid scanning spectrophotometer. The process involves the following four steps and a precipitate whose composition ratio was dodecyl sulfate : pinacyanol= 1 : 1 was obtained as the final product:

(Remark: Graphics omitted.)

where D and S are the dye and detergent molecules respectively. The forward rate constants have been calculated to be 6×105 (M s)−1 for [S]0=0.05–0.1 mM in the second step and 1.2×102–3.9×10−3 s−1 for [S]0=0.05–1.0 mM in the third step.
Semi-empirical SCF-MO Studies of Pd(II)- and Hg(II)-Ethylene Complexes, the Oxymercuration and the Wacker Reaction
Authors: Sakaki Shigeyoshi , Kato Hiroshi , Kanai Hiroyoshi , Tarama Kimio
Published: July 2006

Using the modified CNDO MO method, the electronic structures of Pd(II)- and Hg(II)-ethylene complexes have been studied successfully. Our MO calculations have shown that the nucleophilic attack of OH− on ethylene was accelerated by Pd(II) and Hg(II), and that the acceleration by Hg(II) was larger than that by Pd(II), these results agree well with those of the experiments. The cis-attack of OH− in the oxymercuration has also been discussed by the use of the results obtained by the MO calculations. The mechanism of the cis-type four-center addition of OH− to ethylene in the Wacker reaction, which was supposed by Henry and Jira et al. in spite of any direct evidence, has been supported by the MO calculations. Our calculations have been able to explain the Markovnikoff rule in the Wacker reaction and in the oxymercuration of propylene.
The Thermal [2+2] Cycloaddition of 1-Halo-2-(9-fluorenylidene)ethylene to Afford Fluorene-9-spiro-1′-[2′-halo-3′-(9-fluorenylidene)-4′-halomethylene]cyclobutane
Authors: Toda Fumio , Motomura Hiroharu , Oshima Hirofumi
Published: July 2006

The thermal [2+2]cycloaddition products of 1-chloro-(II) and 1-bromo-2-(9-fluorenylidene)ethylene (X) were found to be two head-to-tail dimers, fluorene-9-spiro-1′-[2′-chloro-3′-(9-fluorenylidene)-4′-chloromethylene]cyclobutane (VI) and its bromo-analog (XI) respectively.
Preferential Precipitation of Δ-[Co(en)3]2(d-C4H4O6)3 by Alcohol Addition to the [Co(en)3]3+–d-C4H4O62− Aqueous Systems
Authors: Yoneda Hayami , Takemoto Gen , Sakaguchi Ushio
Published: July 2006

Alcohol addition to the aqueous [Co(en)3]3+–d-tart systems causes the preferential precipitation of Δ-[Co(en)3]2(d-tart)3. The yield lies in between 54–55% under experimental conditions employed.
A Novel Type of Penta-Coordinated Iron(III) Complex FeCl[SSeCNR2]2 (R=CH3, C2H5)
Authors: Nakajima Shunji , Tanaka Toshio
Published: July 2006

The titled compounds were prepared, and the magnetic susceptibility and electronic spectrum were measured; the two weak bands observed in the near-infrared region are assigned as spin-forbidden d-d bands.
Normalization of Potentials in Propylene Carbonate, Ethylene Carbonate, N,N′-Dimethylformamide, and Dimethyl Sulfoxide to the Water Scale Studied by Polarographic Method
Authors: Matsuura Niro , Umemoto Kisaburo , Waki Masako , Takeughi Zen’ichi , Omoto Mariko
Published: July 2006

The polarographic behavior of alkali metal ions were studied in propylene carbonate (PC), ethylene carbonate (EC), water, N,N′-dimethylformamide(DMF), and dimethyl sulfoxide(DMSO). The polarographic half-wave potentials measured in these solvents against an aqueous saturated calomel electrode(SCE) were normalized to the potential of SCE in aqueous system by making corrections of potential required for transfer of rubidium ion from water to these solvents. The free energies of transfer of rubidium ion from water to other solvents were calculated by the application of the modified Born equation. The potential series on the normalized potential scale were given in the order DMSO<DMF<water<PC<EC, indicating that the metal ion-solvent interaction increases with increasing the electron donor property of the solvent. The solvent shifts in potential calculated by the application of the modified Born equation disagreed with the experimental results. In order to fit well the calculated solvent shifts in potential with the experimental results, following values of liquid junction potential must be assumed for these solvents; +0.090 V for DMSO, +0.085 V for DMF, +0.004 V for PC, and −0.064 V for EC against the aqueous phase.
PECULIARITY IN THE FORMATION OF THE NITRILE-ESTERS OF DICARBOXY-GLUTACONIC ACID
Authors: Urushibara Yoshiyuki
Published: July 2006

From the results of eight reactions it was deduced that the four compounds,

XYC=CH–CNaX′Y′,

X′Y′C=CH–CNaXY,

X′Y′C=CH–CNaX′Y′,

XYC=CH–CNaXY,

can be produced in the condensation of the ethoxymethylene compound XYC=CHOC2H5 with the sodio-methylene compound CHNaX′Y′, where each of X, X′, Y, and Y′ represents either –CN or –COOC2H5.
STUDIES ON THE ENZYMES OF SILKWORM. I
Authors: Mori Motohichi
Published: July 2006

1. The optimal temperatures for the action of amylase obtained from the middle intestine of silkworm have been determined.

2. The optimal hydrogen ion concentration for the amylase action has been determined to be PH=9.4–11.3 at 30–40°C.

3. The amylase charges positively in alkaline reaction, and negatively in acid reaction, the isoelectric point being at about PH=5.7.
SORPTION OF GAS BY MINERAL. II. LAUMONTITE
Authors: Sameshima Jitsusaburo
Published: July 2006

Dehydrated Iaumontite sorbs ammonia but not carbon dioxide. The sorption amount of ammonia varies markedly by the conditions of the dehydration. Same amount of ammonia is sorbed at 25°C. and at 0°C. by a sample. The ammonia combines chemically with dehydrated mineral.
ON THE DISSOLUTION VELOCITY OF OXYGEN INTO WATER. PART III
Authors: Miyamoto Susumu , Kaya Tetsuo
Published: July 2006

(1) The influence of the magnitude of the radius of the tube, through which air is passed, upon the oxidation velocity of sodium sulphite was observed.

(2) The theoretical considerations on the result was described.
Solvent Effects and Hyrogen-bonding Interactions on Absorption and Fluorescence Spectra of 1-Methyl-2-pyridone
Authors: Fujimoto Akira , Inuzuka Kozo
Published: July 2006

The electrostatic solvent effects and hydrogen-bonding interactions on IR and UV absorption and fluorescence spectra of 1-methyl-2-pyridone has been investigated. It was found that the UV absorption and fluorescence bands of 1-methyl-2-pyridone shifted towards the shorter-wavelength region with increasing solvent polarity and that these bands exhibited a blue shift on hydrogen bond formation with alcohols and chloroform. The excited-state dipole moment of 1-methyl-2-pyridone, and the equilibrium constants in the ground and excited states and enthalpy change in the ground state for hydrogen-bond formation between 1-methyl-2-pyridone and ethanol have been determined from the spectroscopic studies.
The Crystal Structure of the 1 : 2 Tetrapropylammonium Guanidinium Bromide Complex
Authors: Taga Tooru , Ohashi Makoto , Osaki Kenji , Miyajima Koichiro , Yoshida Hiromitsu
Published: July 2006

The crystal of the title complex is monoclinic, P21/a with these unit cell dimensions: a=16.16, b=19.18, c=15.46 Å, and β=98°. The crystal structure has layers of hydrogen-bond networks formed by the guanidinium and bromide ions. Two different conformers of the tetrapropylammonium ions are packed between the networks.
Secondary Deuterium Isotope Effects in the Intramolecularly-competing Methoxymercuration of Ethylene-1,1-d2 and cis-2-Butene-2-d1
Authors: Shinoda Sumio , Isemura Masashi , Saito Yasukazu
Published: July 2006

Secondary deuterium isotope effects in the intramolecularly-competing methoxymercuration of ethylene-1,1-d2 and cis-butene-2-d1, determined from the rate ratio (k(β-deuteriomercurial)/k(α-deuteriomercurial)=1.12, 1.06), indicate that the transition state for the methoxymercuration of ethylene and cis-2-butene does not have a symmetrical structure such as a mercurinium ion, but is accompanied by considerable C–O bond formation.
Friedel-Crafts Reaction of Anisole with 2-t-Butyloxirane
Authors: Inoue Masashi , Harada Masatsune , Umaki Nobuyuki , Ichikawa Katsuhiko
Published: July 2006

The title reaction in excess anisole gave a mixture composed of 3-(methoxyphenyl)-2,3-dimethyl-1-butanols (2) (a mixture of ortho and para isomers), 2-p-methoxyphenyl)-2-methybutane (3), and oligomer of 2-t-butyloxirane, while the same reaction in nitromethane gave a product composed of 2 (only the para isomer) and hexylanisoles, but not 3. The reaction sequences to give the products are discussed in terms of step-by-step and concerted alkylation mechanisms.
The Reactions of 2-(Trimethylsiloxy)furans with Orthocarboxylic Esters, Acetals, and Acylal in the Presence of Lewis Acids
Authors: Asaoka Morio , Sugimura Naoyuki , Takei Hisashi
Published: July 2006

The reaction of 2-(trimethylsiloxy)furan (1) with orthocarboxylic esters, acetals, and acylal in the presence of Lewis acids afforded the corresponding 4-substituted 2-buten-4-olides. The reaction of 5-methyl-2-(trimethyl-siloxy)furan with orthocarboxylic esters gave unstable 2-substituted 3-penten-4-olides as major products; these gave 2,5-alkanediones upon hydrolysis. The furan (1) also reacted with 1,1-diacetoxy-2-butene to give a mixture of 5-acetoxy-2,6-octadien-4-olide and 7-acetoxy-5-methyl-2,6-heptadien-4-olide. From the former compound, nigrosporalactone was synthesized.
The Transformations of Terpene Ketones by Oxygen. I. The Autoxidation of Fukinone
Authors: Horinaka Akio , Naya Keizo
Published: July 2006

Fukinone, possessing a cisoid enone system, is susceptible to air oxidation. The oxidation products have been extensively examined and have been established as including diastereomeric epoxides, a hydroxy ketone (petasitolone), a lactol (8β-hydroxyeremophilenolide), and a peroxy hemiacetal. Also, the products were compared with those derived from the autoxidation of pulegone, a monoterpenic analogue of fukinone.
Chemistry of N-Thiosulfinylanilines. I. Reactions of Sterically Hindered Anilines with Sulfur Chlorides. Preparation of N-Thiosulfinylanilines
Authors: Inagaki Yoshio , Okazaki Renji , Inamoto Naoki
Published: July 2006

Reaction of 2,4-di-t-butyl-6-methylaniline (3) with disulfur dichloride afforded 2,4-di-t-butyl-6-methyl-N-thiosulfinylaniline (4) as a stable compound in 80% yield. Reaction of 2,4,6-tri-t-butylaniline (1) with disulfur dichloride gave in 70% yield 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene, which in solution, exists as a tautomeric mixture with 2,4,6-tri-t-butyl-N-thiosulnnylaniline (2b) as a minor component. In the reactions with 2,4-di-t-butyl-6-isopropyl- or 2,4,6-trimethylaniline, N-thiosulfinylanilines obtained were unstable at ambient temperature. Aniline 1 reacted with sulfur dichloride to give 2 and the corresponding sulfur diimide and N-sulfinylaniline. The reaction of 4 with the dichloride afforded 4 and the corresponding sulfur diimide.
Chemistry of N-Thiosulfinylanilines. III. Thiosulfinylamine—5H-1,2,3-Dithiazole Equilibrium as Studied by NMR Spectroscopy
Authors: Inagaki Yoshio , Okazaki Renji , Inamoto Naoki , Yamada Koh-ichi , Kawazura Hiroshi
Published: July 2006

Thermodynamic parameters (ΔH=−4.9 kcal mol−1, ΔS=−11.3 cal mol−1 deg−1) were determined for cyclization of 2,4,6-tri-t-butyl-N-thiosulfinylaniline (1b) (the minor component) into 2,4,6-tri-t-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene (1a) (the major component) by means of NMR spectroscopy. Using these values, π-bond of thiosulfinylamino group (–N=S=S) was estimated to be weaker than that of sulfinylamino group (–N=S=O) by, at least, 25 kcal mol−1. The equilibrium ratio [1a]/[1b] is subject to considerable solvent effect, polar solvents favoring the cyclic form (1a). Similarity of the thiosulfinylamine-dithiazole equilibrium to that of azidoimine-tetrazole has been pointed out.
A New Synthesis of Arylacetic Esters Starting from Aromatic Aldehyde by the Use of Methyl (Methylthio)methyl Sulfoxide
Authors: Ogura Katsuyuki , Ito Yoko , Tsughihashi Gen-ichi
Published: July 2006

Methyl (methylthio) methyl sulfoxide was found to react with benzaldehyde in the presence of benzyl tri-methylammonium hydroxide (Triton B), sodium hydroxide, or potassium hydroxide, affording 1-(methylsulfinyl)1-(methylthio)-2-phenylethylene. Treatment of this product with hydrogen chloride in an alcohol gave the corresponding alkyl phenylacetate in high yield. The whole reaction sequence provides a new method for synthesizing phenylacetic esters starting from benzaldehyde. In a similar manner, (alkoxy-, halogen-, or alkyl-substituted phenyl)acetic esters could be synthesized from the corresponding aromatic aldehydes. The present method was shown to be also applicable to the production of (2-thienyl)acetic esters.
Chemistry of Dienyl Anions. I. Crystalline Dienyl Anions by Direct Reaction of Conjugated and Non-conjugated Dienes with Alkali Metals in the Presence of Et3N
Authors: Yasuda Hajime , Ohnuma Yasuo , Yamauchi Michihide , Tani Hisaya , Nakamura Akira
Published: July 2006

Series of acyclic and cyclic dienyl anions were prepared from both conjugated and non-conjugated dienes by direct metalation with alkali metals (Li, Na, K, Rb, and Cs) in tetrahydrofuran in the presence of triethylamine or N,N,N′,N′-tetramethylethylenediamine. Eight different dienyl anions of open chain or cyclic structures were isolated as crystals. All the acyclic potassium dienides of pentadienes, 2-methylpentadienes, 3-methylpentadienes, hexadienes and 2,4-dimethylpentadienes gave the corresponding 1,3-dienes upon hydrolysis, while the potassium cyclic dienide of cycloheptadienes and cyclooctadienes gave 1,4-dienes exclusively. The result of methylation of dienyl anions with methyl iodide agreed with that of hydrolysis. The reaction path for formation of these dienyl anions was studied based on the carbon skeleton and the molar ratio of the reduced diene dimers produced together with the dienyl anions. Selective oxidative coupling of the dienyl anions occurred with CuX or CuX2 to give linear tetraenes in good yield.
The Characterization of the Hydroxyl Surface of Silica Gel
Authors: Kondo Seiichi , Tomoi Kazuo , Pak Chynryon
Published: July 2006

The properties of silica gel were studied as a function of the hydrothermal treatment of hydrogel by means of the nitrogen-adsorption isotherm, the mechanical strength, thermodilatometry, and infrared spectroscopy. As a result, the number of contact points between primary particles of silica was found to decrease, and closed pores were found to be produced, by this treatment. The analysis of the infrared absorption spectra of the OH groups of this material showed that there are three kinds of OH groups in silica gel; (1) free OH groups on the outer surface of primary particles, which can adsorb molecules easily, (2) weakly perturbed OH groups inside closed pores, and (3) strongly hydrogen-bonded OH groups on the surface around the contact points. The relative concentration of these OH groups changes drastically upon the hydrothermal treatment; this is in accord with the change in the macroscopic properties mentioned above.
Diffusion Thermoeffect in Gases (The Dufour Effect)
Authors: Boushehri Ali , Abbaspour A
Published: July 2006

A study of the Dufour effect was made for four different gas mixtures: SF6–N2O, SF6–N2, SF6–CO2, and He–CO2. Measurements were made at 300 K under 700 Torr. The values of the thermal diffusion factor were calculated for the above mixtures from experimental data on the basis of the thermodynamics of irreversible processes. A theoretical study was made also to calculate the thermal diffusion factor from kinetic theory.
Magnetic and Spectral Properties of Binuclear Nickel(II) Nitrato and Acetato Complexes of Tridentate Schiff Bases Derived from Salicylaldehydes and N-Substituted Trimethylenediamines
Authors: Tokii Tadashi , Emori Shuji , Muto Yoneichiro
Published: July 2006

A new series of binuclear Ni(II) complexes with the empirical formula Ni(5-Y-sal·pr·NRR′)X has been prepared by the reaction of the parent complexes, Ni(5-Y-sal·pr·NRR′)2 with metal salts NiX2, where 5-Y-sal·pr·NRR′= Schiff base ligand derived from 5-substituted salicylaldehyde and N-substituted trimethylenediamine, R=H or CH3, R′=CH3, Y=H or Cl and X=NO3 or CH3COO. The nature of the complexes has been confirmed to be dimeric on the basis of the results of molecular weight, magnetic and spectral measurements. The values of exchange integral, J=−10–−15 cm−1, have been evaluated for the Ni(II) complexes from their temperature dependences of magnetic susceptibilities. The antiferromagnetic property has been discussed in terms of structural considerations. For comparison, the corresponding Cu(II) complexes Cu(5-Y-sal·pr·NRR′)X have been prepared and investigated.
The Thermal Decompositions of Dialkyl Peroxides
Authors: Uetake Kazuya , Ueda Kenji , Sakikawa Noriyuki
Published: July 2006

With the purpose of obtaining information needed for hazard prevention, pure liquid dialkyl peroxides (di-t-butyl peroxide (1), bis(1-methyl-1-phenylethyl) peroxide (2), t-butyl 1-methyl-1-phenylethyl peroxide (3), 2,5-bis(t-butyldioxy)-2,5-dimethylhexane (4)) were subjected to thermal-decomposition experiments, in which thermal analyses were conducted by the use of a thermogravimetry (TG)-differential scanning calorimetry (DSC) apparatus equipped with a pinholed pan with a minute pinhole. From the DSC curves recorded, we obtained the decomposition temperature of Samples 2, 3, and 4, as a constant value for each sample, and the maximum exothermic peaks at the optimum pinhole diameters (0.07–0.2 mm). The heats of decomposition obtained could be considered appropriate, as they roughly agreed with the estimated value, on the other hand, 1 shows no exothermic peak under these condition. Plotting by the Goats-Redfern method based on the TG-curve data (2, 3, and 4) gave reaction orders of more than unity, activation energies of 33–37 kcalth/mol, and frequency factors of 1016–1018 s−1. It is conceivable that these results could be derived by virtue of the TG–DSC curves that were suitable in obtaining thermochemical parameters. In other words, the analysis method introduced in this paper was found to be an efficient one for liquid peroxides that are difficult to analyze by a conventional TG–DSC method.
Adduct Formation of the Mixed Copper(II) 2-Thenoyltrifluoroacetonate-3-isopropyltropolonate Chelate with Tributyl Phosphate in Solvent-extraction Systems Containing These Ligands
Authors: Sekine Tatsuya , Tosaka Teruyuki
Published: July 2006

From the extraction data of copper(II) in a perchlorate solution into carbon tetrachloride containing 2-thenoyltrifluoroacetone (Htta), 3-isopropyltropolone (Hipt), and tributyl phosphate (tbp), the formation of an adduct mixed chelate, Cu(tta)(ipt)(tbp), together with the Cu(tta)2, Cu(tta)2(tbp), Cu(tta)(ipt), and Cu(ipt)2 species, was concluded, and the formation constant of this adduct mixed chelate was calculated.
Synthesis of (S,S)-2-Amino-3-phenylbutyric Acid
Authors: Tsuchihashi Gen-ichi , Mitamura Shuichi , Ogura Katsuyuki
Published: July 2006

(S,S)-2-Amino-3-phenylbutyric acid was synthesized starting from diethyl (R)-(1-phenylethyl)malonate which was obtained by desulfurization of the adduct in the stereoselective Michael reaction of (R)-styryl p-tolyl sulfoxide with diethyl malonate. This synthetic amino acid was identical with the 2-amino-3-phenylbutyric acid obtained by degradation of bottromycin and thus the absolute configuration of the naturally occurring amino acid was proved to be (S,S).
Kinetics of the Aminolysis of α-Chloropropionic Acid. Reactivity of Aliphatic Amines
Authors: Ogata Yoshiro , Yamauchi Yuya
Published: July 2006

The kinetics for the reaction of α-chloropropionic acid with some amines (methylamine, dimethylamine, trimethylamine, ethylamine, and diethylamine) and ammonia have been studied in an aqueous solution. The reactivity of amines is discussed on the basis of the Swain-Scott and Taft equations.
Interaction of Excited Lithium Atom with Molecular Hydrogen. I. Preliminary Potential Energy Surfaces in an OVC MCSCF Approximation
Authors: Mizutani Kimiko , Kuribara Yoshihiro , Hayashi Kazuko , Matsumoto Shiro
Published: July 2006

Potential energy surfaces were computed for the Li–H2 system of C2V symmetry, which dissociates to a normal hydrogen molecule and a lithium atom either in its ground state or in the 2P excited state, in order to get an idea of the quenching process of the atom by the molecule. The potential surfaces crossed in a line and two shallow minima appeared on the 2B2 surface. Natural orbital analysis and electron density maps gave information on the charge transfer character of the interaction of the excited atom with the molecule.
Singlet Excitation Energy Migration in the Glassy Organics Blended with Polymer
Authors: Sano Yumiko , Shirota Yasuhiko , Mikawa Hiroshi
Published: July 2006

Studies have been made of the singlet excitation energy migration of 1,3-diphenyl-5-(p-chlorophenyl)-2-pyrazoline in a glassy state blended with an ethylene-vinyl acetate copolymer by the fluorescence quenching method. The results are discussed in terms of the simple random energy migration model, showing that the efficiency of the singlet excitation energy migration does not differ between the glassy state and the polymer blend system.
Ultraviolet Photoelectron Spectra of Crown Ethers
Authors: Kajitani Masatsugu , Sugimori Akira , Sato Naoki , Seki Kazuhiko , Inokuchi Hiroo , Harada Yoshiya
Published: July 2006

The He I spectra of 12-crown-4, 15-crown-5, 18-crown-6, dicyclohexyl-18-crown-6, and dibenzo-18-crown-6 have been measured. The features of the spectra are similar except for the case of dibenzo-18-crown-6, where two lower IP bands correlated with the highest occupied π-orbitals of benzene are observed together with the bands due to the polyether ring. By the aid of the CNDO/2 calculation, the lower IP bands of the spectra have been assigned to the MO’s mainly due to the equatorial or axial type non-bonding orbitals of the oxygen atoms of the polyether rings.
A Study on Electronic Excited States of Iridium(III) Complexes Containing Bipyridine and Phenanthroline Ligands. Solvent Effect on Triplet-Triplet Absorption Spectra
Authors: Ohashi Yukako , Kobayashi Takayoshi
Published: July 2006

In order to study the solvent effect on the lowest excited state of of cis-[IrCl2L2]Cl (L=2,2′-bipyridine, 1,10-phenanthroline, and 4,7-dimethyl-1,10-phenanthroline), the triplet-triplet absorption spectra (15000 cm−1—27000 cm−1) were measured by the use of N,N-dimethylformamide–water mixed solvents. For the triplet-triplet spectra of the three iridium complexes, remarkable spectral changes were observed with the change of the solvent polarity. An SCF calculation of the triplet-triplet transitions was carried out for free bipyridine and free phenanthroline. By comparing the calculated results and the observed spectra, the solvent effect can be interpreted in terms of a model invoking dπ*-ππ* interaction, as proposed by Crosby. The lowest triplet state of [IrCl2(phen)2]Cl is predominantly a dπ* state in 95% v/v DMF–water, but in water, by the reversal of the state ordering, the lowest state becomes a ππ* state. Furthermore, a quite similar solvent effect which was observed on the lowest triplet state of [IrCl2(bpy)2]Cl is discussed; this state is not expected to have a dπ*-ππ* interaction.
Molecular Structures of Adducts of Benzoyl Isothiocyanate and Hydrazones Determined by the X-Ray Diffraction Method
Authors: Fukutani Yasuhide , Tsukihara Kumiko , Okuda Yukio , Fukuyama Keiichi , Katsube Yukiteru , Yamamoto Iwao , Gotoh Haruo
Published: July 2006

X-Ray diffraction analysis was used to establish the molecular structures of some adducts of benzoyl isothiocyanate with hydrazones: benzaldehyde 4-benzoyl-2-phenylthiosemicarbazone (1), 2-benzoylimino-3,5-diphenyl-2,3-dihydro-1,3,4-thiadiazole (2), and 5-benzoylimino-2,2-dimethyl-4-phenyl-1,3,4-thiadiazolidine (3). In adducts 2 and 3, a strong intramolecular interaction between sulfur and carbonyl oxygen atoms has been found. The S…O distance is 2.56 Å for 2 and 2.76 Å for 3, and the oxygen atom lies approximately in the plane defined by the sulfur atom and the two carbon atoms bonded to the sulfur atom. The absence of a characteristic absorption due to a carbonyl group in the IR spectra of 2 and 3 reflects the intramolecular interaction. The crystal of 1 is triclinic, space group P\barl, with a=12.041, b=8.414, c=11.298 Å, α=116.13, β=103.39, γ=103.27°; that of 2 is monoclinic, space group P21/c, with a=20.842, b=3.977, c=21.120 Å, β=103.55°; and that of 3 is monoclinic, space group P21 with a=12.559, b=6.910, c=10.283 Å, β=115.46°. The structure has been refined by the block-diagonal least-squares method to R=0.089 with 2508 reflections for 1, to R=0.088 with 1872 reflections for 2, and to R=0.098 with 1031 reflections for 3.
Crystal Structures of Mixed Ligand Copper(II) Complexes Containing l-Amino Acids. I. l-Asparaginato-l-histidinato-copper(II) and Its Hydrate
Authors: Ono Taizo , Shimanouchi Hirotaka , Sasada Yoshio , Sakurai Takeshi , Yamauchi Osamu , Nakahara Akitsugu
Published: July 2006

Two copper complexes containing l-histidine and l-asparagine crystallize from aqueous solution at pH 7.0. Both crystals are monoclinic, space group P21. l-Asparaginato-l-histidinatocopper(II): a=10.913(3), b=12.911(4), c=10.206(3) Å, β=113.83(2)°, Z=4. l-Asparaginato-l-histidinatoaquacopper(II) trihydrate: a=12.654(4), b=11.623(4), c=5.931(2) Å, β=100.47(3)°, Z=2. In both structures, four coordinating atoms in an approximately planar arrangement around copper are the α-amino and imidazole δ-nitrogen atoms of l-histidine and α-amino nitrogen and α-carboxyl oxygen of l-asparagine. The fifth coordination site is occupied by the α-carboxyl oxygen of l-histidine. Difference between the two complex crystals is found at the sixth coordination site; a water molecule is coordinated in the hydrated crystal to complete a distorted octahedral environment, while in the anhydrous crystal this site is unoccupied so that the geometry of the complex is square-pyramidal.
Calculations of the Solvent Effects on Some Nitrogen Chemical Shifts
Authors: Ando Isao , Jallali-Heravi M , Kondo Masahiro , Watanabe Shosuke , Webb G A
Published: July 2006

Nitrogen screening constants are calculated by the sum-over-states method using INDO/S parameters and by the finite perturbation procedure employing INDO parameters. The solvaton model is employed to describe changes in nuclear screening as a function of the dielectric constant of the medium. The calculated variations of nitrogen screening are in reasonable agreement with the available experimental data. The effects on screening of hydrogen bonding are included in the sum-over-states calculations by means of dimer models.
The Halomercury(II)-assisted Aquation of the Bromopenta-cyanocobaltate(III) Anions
Authors: Iida Masayasu , Yamatera Hideo
Published: July 2006

The aquation of the bromopentacyanocobaltate(III) ion was carried out in the presence of several kinds of hard acids or halomercury(II) complexes. The hard acids(H+, Na+, and Mg2+) had small effects, while the addition of mercury(II) halides significantly accelerated the aquation. The effect of mercury(II) halides was attributed to the monohalomercury(II) cations, which were formed in a small amount by the dissociation of the dihalomercury(II) complexes. The effect of the dihalomercury(II) complexes was also studied in the presence of an excess of sodium halide. The rate constant for halomercury(II)-assisted aquation was expressed by:

k obsd=k0+k1[HgX+]+k2[HgX2], X−=Cl−,Br−.

The values of k1 and k2 obtained (k1=1.6×104 mol−1 dm3 s−1, k2=1.0 mol−1 dm3 s−1, for X−=Cl−; k1=2.0×104 mol−1 dm3 s−1, k2=1.6×10−1 mol−1 dm3 s−1, for X−=Br−) were compared with the stability constants for the mercury(II) complexes formed by the combination with Br−.
The Isolation of 227Ac from 231Pa and the Gamma-ray Spectra of 231Pa, 227Th, and 223Fr
Authors: Mitsugashira Toshiaki , Yamana Hajimu , Suzuki Shin
Published: July 2006

A method for the isolation of 227Ac and its daughter nuclides from 231Pa was established. The γ-ray spectra of 231Pa, 227Th, and 223Fr were investigated, and the γ-ray tables of these nuclides were presented. A decay scheme of 223Fr was corrected so as to explain these γ-ray data.
Region of Formation of Iron(III) Hydrogen Orthophosphate and Structural Changes in Humid Atmospheres
Authors: Tsuhako Mitsutomo , Oyama Chinuyo , Matsuo Tsuneo , Motooka Itaru , Kobayashi Masamitsu
Published: July 2006

The conditions of formation of the A and B forms of Fe(H2PO4)3 by the reaction of Fe2O3 and H3PO4 have been established, and the thermal changes and structural changes in humid atmospheres investigated. 1) The A and B forms of Fe(H2PO4)3 were readily formed by secondary heat treatment at 150 °C and 125 °C, respectively. 2) The forms of Fe(H2PO4)3 were largely dependent on the heating rate in the primary heat treatment, i.e., at a mean heating rate less than 7 °C/min the A form predominated, whereas above 60 °C/min the B form predominated. A heating rate between 7 and 60 °C/min gave a mixture of the A and B forms. 3) A close relationship between the water content of the primary product and yields of the A and B forms of Fe(H2PO4)3 was found, i.e., only the B form was obtained when the water content of the primary product was less than 7%, while the A form was readily formed when the water content was greater than 11%. 4) Heating the primary product under various degrees of humidity enabled the formation of Fe(H2PO4)3 to be investigated. The effect of heating atmosphere was small except under vacuum. 5) The structural changes of the A and B forms of Fe(H2PO4)3 under several humid atmospheres are summarized as follows:

(Remark: Graphics omitted.)
Solvation of Anions in Solvent Mixtures as Deduced from the Rates of the Finkelstein Reaction
Authors: Kondo Yasuhiko , Nishikata Akira , Yoshioka Akiteru , Tokura Niichiro
Published: July 2006

The Finkelstein reaction has been studied in five dipolar aprotic–dipolar aprotic solvent mixtures and one protic-dipolar aprotic solvent mixture. The theoretical equations for the rate constant as a function of solvent composition derived previously have been reformulated in terms of the solvent exchange model on the solvation site, taking into account the two main features of solvation: the number of the solvation sites on the solvent molecule and the equilibrium constant for the solvent exchange process. The results obtained previously, together with present results, are comprehensively discussed and the solvent mixtures are classified into four groups from the viewpoint of solute-solvent interaction in the region near the ion, using derived theoretical equations.
Effect of Complexation by Crown Ethers on Anisochrony of Diastereotopic Groups in NMR Spectra
Authors: Ando Nobuharu , Yamamoto Yukio , Oda Jun’ichi , Inouye Yuzo
Published: July 2006

Anisochrony of geminal methyls in alkylamines bearing a chiral center in the molecule is affected by complexation with crown ethers, which amplify the chemical shift non-equivalence in NMR. The resolved signal of gem-methyls in valine methyl ester were unequivocally assigned to pro-R and pro-S methyl groups respectively.
Phenanthro[4,5-bcd]furan Derivatives. V. The Cyclization of (Dibenzofuran-1-yl)acetic Acid Derivatives
Authors: Horaguchi Takaaki , Abe Teishiro
Published: July 2006

The cyclization of (6-methoxy-1,2,3,4-tetrahydrodibenzofuran-1-yl)acetic acid (3b) and (6-methoxy-1,2,3,4,4a,9b-hexahydrodibenzofuran-1-yl)acetic acid (5) to the corresponding phenanthro[4,5-bcd]furans have been examined. The cyclization of 3b was difficult, while that of 5 was easy. The difficult cyclization of 3b has been attributed to strains in the reaction intermediate.
A Convenient Method for the Preparation of 4-(3-Halogenatedphenyl)-and 4-(3,5-Dihalogenatedphenyl)-4-oxobiityric Acids
Authors: Jojima Teruomi , Takeshiba Hideo , Kinoto Takao
Published: July 2006

Various 4-(3-halogenatedphenyl)- and 4-(3,5-dihalogenatedphenyl)-4-oxobutyric acids were synthesized by the nuclear halogenation of the corresponding 4-aryl-4-oxobutyric acids in the presence of an excess of aluminum chloride. In most of these reactions, consecutive succinoylation and halogenation of the aromatic compounds were carried out in one pot operation.
The Polymerization of β-Propiolactone by Calcined Synthetic Hydrotalcite
Authors: Nakatsuka Takuo , Kawasaki Hitoshi , Yamashita Shinzo , Kohjiya Shinzo
Published: July 2006

The calcination of synthetic hydrotalcites of different compositions gave aluminium magnesium double oxides with strong basic sites and a high catalytic activity towards the polymerization of β-propiolactone. The strong basic sites were determined and compared with the apparent polymerization rates, suggesting that the strong basic sites are active sites towards the reaction.
On the Phase Transitions in Ammonium Hexafluoroaluminate(III)
Authors: Moriya Keiichi , Matsuo Takasuke , Suga Hiroshi , Seki Syûzô
Published: July 2006

The heat capacities of (NH4)3[AlF6] were measured between 11 and 300 K with an adiabatic calorimeter. Two anomalies were found at (193.0±0.3) K and (220.79±0.05) K. The enthalpy and entropy of the phase transitions are (790±150) J mol−1 and (4.2±0.8) J K−1 mol−1 for the former, and (4030±150) J mol−1 and (18.5±0.7) J K−1 mol−1 for the latter, respectively. The total anomalous entropy, (22.7±1.5) J K−1 mol−1, is in agreement with R In 16=23.05 J K−1 mol−1 predicted by a model involving orientational disorder of the hexafluoroaluminate(III) and the ammonium ions. Discontinuities in fluorine T1 and T1ρ at 221 K by pulse NMR measurement also support this model. The potential barrier height of the hindered rotation of the NH4+ ion was estimated to be 7 kJ mol−1 from the heat capacity data. The intermediate phase undercooled and coexisted with the low temperature phase in a limited range of temperature. The upper phase transition is of the first order but the anomalous heat capacity follows the Landau theory of the phase transitions of the second kind. The high symmetry of the crystal structure of the present crystal at room temperatures in comparison with that of the alkali cryolites was discussed in terms of the hydrogen bonding, molecular disorder and packing consideration.