bluuebunny/crossref_metadata_2025 huggingface dataset:
Resonance Energies of Annulenes and Radialenes
Authors: Aihara Jun-ichi
Published: July 2006

Resonance energies of annulenes and radialenes were estimated on the basis of the π-bond energies of infinitely large annulene and radialene, respectively. The widely accepted Hückel’s (4n+2)π rule was verified for annulenes, whereas radialenes were substantially nonaromatic regardless of the number of π-electrons.
The Stereochemistry of the Reaction of Hydrogen Bromide with Cyclohexene and 1-Methylcyclohexene in the Presence of Oxygen
Authors: Miyajima Shingo , Ichihara Sadao , Simamura Osamu
Published: July 2006

The reaction of hydrogen bromide with cyclohexene or 1-methylcyclohexene in the presence of oxygen, followed by reduction with lithium aluminium hydride afforded trans-2-bromocyclohexanol or t-2-bromo-1-methyl-r-1-cyclohexanol. These findings show that oxygen attacks intermediate bromocyclohexyl radicals formed by addition of a bromine atom to a double bond exclusively on the side opposite to the bromine substituent. Mechanistic implications are discussed.
Structural Studies of Tryptophan Metabolites by X-ray Diffraction Method. III. The Crystal and Molecular Structure of 5-Methoxyindole-3-acetic Acid
Authors: Sakaki Toshimasa , Wakahara Akio , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

The crystal structure of 5-methoxyindole-3-acetic acid (5-MIAA) has been solved by application of the direct method with symbolic addition procedure. 5-MIAA, colorless transparent prism, is monoclinic, space group C2/c, with lattice parameters: a=34.461(9) Å, b=6.150(5) Å, c=9.480(5) Å, β=96.14(2)°, Z=8. The molecules are hydrogen-bonded into dimers related by the center of symmetry, which are held together in an infinite double-layered sheet structure perpendicular to the a-axis with N–H···O hydrogen bond between indole nitrogen and carboxyl oxygen atoms. The methyl groups of adjacent molecules contact to each other by van der Waals forces. The conformation of the side-chain is quite distinguishable from that of indole-3-acetic acid. The dihedral angle between carboxyl and indole planes is 59.5° in this molecule, whereas that is 90.0° in indole-3-acetic acid, and the carboxyl group sticks out to be perpendicular to the indole plane.
ESR Studies of Reduced Molybdovanadophosphoric Heteropoly Acids. II. Homogeneous Reduction
Authors: Otake Masayuki , Otaki Tadaaki
Published: July 2006

ESR spectra of the chemically reduced molybdovanadophosphoric heteropoly acids (H3+xMo12−xVxPO40·nH2O, where x=1 and 2) were observed in the solution and glassy state in various organic solvents. On addition of equimolar amounts of reductants such as SnCl2·2H2O, HSCH2CH2SH, and CH3SCH3, a transient ESR signal(B) appeared with eight hfs lines referred to as V(IV), I=7⁄2, and with =1.96 and =−0.83×10−2cm−1. However, it disappeared within ca. 5 hr at 20°C and another signal(C) with =1.962 and =−1.00×10−2 cm−1 gradually increased in intensity. The hyperfine coupling constant of the transient species was thus unusually small as compared with that of the ordinary V(IV) species and the C species. The mechanistic pathways of the reduction were discussed. The splitting observed in the low-field parallel components of the B signal was satisfactorily explained by a “geometrical charge isomerism” characteristic of the structure of the heteropoly anion. The origin of the unusually small hfs constant was discussed in the light of its molecular structure.
Aromatic Thiocyanation by a Mixture of Antimony(V) Chloride and Lead(II) Thiocyanate
Authors: Uemura Sakae , Onoe Akira , Okazaki Hajime , Okano Masaya
Published: July 2006

Alkyl- and halobenzenes give thiocyano-derivatives when treated with a mixture of SbCl5 and Pb(SCN)2 in CCl4. The reaction proceeds via in situ formation of ClSCN from SbCl5 and Pb(SCN)2 followed by its attack on aromatic compounds catalyzed by SbCl5, the reaction species being SCN+SbCl6−.
Reactions of 2,4,6-Tri-t-butylnitrosobenzene with Grignard Reagents
Authors: Inagaki Yoshio , Okazaki Renji , Inamoto Naoki
Published: July 2006

Reactions of 2,4,6-tri-t-butylnitrosobenzene (1) with alkylmagnesium halides afforded 6-alkyl-1-hydroxy-imino-2,4,6-tri-t-butyl-2,4-cyclohexadienes (2), 4-alkyl-1-hydroxyimino-2,4,6-tri-t-butyl-2,5-cyclohexadienes (3), and N-alkyl-2,4,6-tri-t-butylanilines (4) depending on the Grignard reagents used. The distribution of the reaction products indicated that the oximes were formed via an attack of the anionic species on the ortho- and the para-carbons, respectively, to the nitroso group, but that the N-alkylanilines via a free radical mechanism involving an electron transfer from the Grignard reagent to 1. The free radical mechanism was confirmed in the case of t-butylmagnesium chloride by trapping the t-butyl radicals as 1-t-butoxyimino-2,4,4,6-tetra-t-butyl-2,5-cyclohexadiene (8). Such a mechanistic difference has been explained in terms of the difference in electron affinities of the free radicals derived from Grignard reagents.
Surface Tension of Aqueous Solutions of Disodium Monoalkyl Phosphates and Their Mixtures
Authors: Nakagaki Masayuki , Handa Tetsurou
Published: July 2006

Disodium mono-dodecyl, mono-tetradecyl, and mono-hexadecyl phosphates were synthesized and the surface tension of aqueous solutions of each disodium monoalkyl phosphate (SAP) and of their mixtures were measured. On the basis of the surface tension values thus obtained, the influence of the hydrocarbon chain length of SAP and the effect of the mixing of SAP on the adsorption and the micelle formation were discussed. A modified Szyszkowski equation was derived from the Gibbs adsorption equation and the modified Langmuir adsorption equation by using the activity instead of the concentration. The modified Szyszkowski equation gave calculated values which were in good agreement with the experimental values of the surface tension. It was also found that the energy of adsorption per methylene group, ω, is 682 cal/mol. In mixed solutions, the modified Szyszkowski equation was used to obtain results in good agreement with the measured values of the surface tension, assuming an ideal mixing of SAP in the adsorption layer. Further, the change in the standard free energy was calculated for the micelle formation for each SAP from the hypothetical standard state of the hydrated monomer in solution; it gave the energy of micelle formation per methylene group, ωm, is 613 cal/mol. The theoretical equation to give the cmc of SAP, was obtained also, assuming the ideal mixing of SAP in the mixed micelle phase; it was proved to be in good agreement with the experimental values of the cmc.
Electron Spin Resonance of Oriented Solid of Isocyanic Acid Irradiated with γ-Rays
Authors: Hirai Hidefumi , Fujiwara Masato
Published: July 2006

Free radicals in the γ-irradiated solid of isocyanic acid at −196 °C have been studied by electron spin resonance (ESR) spectroscopy at −196–−100 °C. An oriented solid of isocyanic acid was prepared by solidification of isocyanic acid around an aluminum rod with cooling for the measurement. The ESR spectra consisted of a pair of triplets and a pair of sextets, when the longitudinal axes of the oriented solid were parallel and perpendicular, respectively, to the dc magnetic field. The absorptions were assigned to an anion radical (HNCO−) by analysis of anisotropy of the spectrum and by deuteration of isocyanic acid. The observed constants were: g⊥=2.0025, g⁄⁄=1.9985; Ax(N)=21.2 G, Ay(N)=24.8 G, Az(N)=21.8 G. The anion radical was assumed to be preferentially oriented in the oriented solid, taking two orientations whose g⁄⁄ axes were perpendicular both to each other and to the longitudinal axis of the oriented solid.
Reaction of Iron(III)-Form Ion Exchanger with Acetylacetone
Authors: Ohzeki Kunio , Ikeuchi Mayumi , Kambara Tomihito
Published: July 2006

It was found that ferric ions are removed from resin by acetylacetone(Hacac) to form trisacetylacetonatoiron-(III), Fe(acac)3. By the addition of a small amount of pyridine-water mixture to the iron(III)-form resin in acetylacetone milieu, the ferric ions are quantitatively removed from the resin, and in their place the pyridinium ions are adsorbed onto it. The reaction was successfully applied to the synthesis of Fe(acac)3 in over 95% yield.
Polarogpraphy of Europium(III) in Acetonitrile in the Presence of Thiocyanate and Halide Ions
Authors: Aihara Makoto , Misumi Seizo
Published: July 2006

Studies were carried out on the polarographic behavior of europium in acetonitrile in the presence of SCN−, Br−, I− and Cl−. Two reduction waves were found in the Eu(III)–SCN− system, one corresponding to the reduction of [Eu(NCS)6]3− and the other to the reduction of [Eu(NCS)2]. In the Eu(III)–Br− system, the reduction potential of Eu(III)–bromide complex species was more positive than that of the [HgBr4]2−/Hg couple. In the Eu(III)–I− system, iodide ions were oxidized in acetonitrile by europium(III). The formation constants of Eu(III)–SCN− system were found to be: logβ6=24.4 for [Eu(NCS)6]3− and logβ2=6.0 for [Eu(NCS)2. The degree of complexation of europium(III) and mercury(II) with bromide ion was also determined.
A-Subustituted 5β-Steroids. VI. trans-Sn2′ Reaction in Acylolysis of 4β-Bromo-3-keto-5β-steroids
Authors: Takahashi T Tomoyoshi , Satoh J Yasuo
Published: July 2006

A new type of SN2′ reaction in which the nucleophile enters to the leaving group occurs in the acylolysis of 4β-bromo-3-keto-5β-steroids (1) to give 2α-acyloxy-3-keto-5β-steroids (2) as a product. This reaction pathway was observed by NMR and by tlc.
Ionic Equilibria in Mixed Solvents. XI. A Critical Survey of Hydroxo Complexes of Beryllium in Aqueous and Aqueous Mixed Solvents
Authors: Tsukuda Hitoshi , Kawai Takayoshi , Maeda Masunobu , Ohtaki Hitoshi
Published: July 2006

Hydrolytic reactions of beryllium ion were studied in water-methanol, water-ethanol, and water-acetone mixtures, 0.2 mole fraction of an organic component being contained. In all the solutions containing 3M LiClO4 as an ionic medium at 25 °C, we found the Be2OH3+, Be2(OH)22+, Be3(OH)33+, and Be(OH)2 complexes. However, in a supplementary work in a 3M LiClO4 aqueous medium in which the solution had been equilibrated with precipitates of beryllium hydroxide and the supernatant was subjected to titration, we found Be6(OH)84+ instead of Be(OH)2. From a very slow equilibrium observed in the high pH region, we concluded that the Be(OH)2 complex formed by the addition of an alkaline solution gradually polymerizes to Be6(OH)84+ by releasing some OH− ions. Through these observations a critical survey is described for the species reported by various authors. The solvent effect on the formation constants of hydroxo complexes is also discussed.
Negative Photoconduction in Solution of Aromatic Amine and Benzoquinone by Flash Excitation
Authors: Nakata Jun-ichi , Imura Takeshi , Kawabe Kazuo
Published: July 2006

The conductivity of a solution of benzoquinone and TMPD decreased after being subjected to flash excitation. This is attributed to the decrease of free ions due to the equilibrium shift produced by photo-induced disappearence of the ion pair.
Molecular Vibrations and Force Fields of Alkyl Sulfides. XI. C–S Stretching Vibrations of Some Simple Aliphatic Sulfides
Authors: Ohsaku Masaru
Published: July 2006

Infrared spectra of alkyl sulfides were measured. Some correlations of the C–S stretching frequencies to the molecular conformations were proposed.
The Effect of Partial Deuteration on the Phosphorescence Lifetime of N,N,N′,N′-Tetramethyl-p-phenylenediamine
Authors: Yoshida Nobutoshi , Ebara Nozomu
Published: July 2006

A position-dependent deuterium effect on the phosphorescence lifetime of N,N,N′,N′-tetramethyl-p-phenylenediamine was found. Aromatic ring protons and methyl protons were shown to contribute to the radiationless transition independently and differently. Important terms in the decay constant are briefly discussed.
Densities and Molar Volumes of Molten Binary PrCl3–KCl, PrCl3–NaCl, PrCl3–CaCl2, NdCl3–KCl, NdCl3–NaCl, NdCl3–CaCl2 Systems
Authors: Mochinaga Junichi , Igarashi Kazuo
Published: July 2006

The densities of PrCl3, NdCl3, PrCl3–KCl, PrCl3–NaCl, PrCl3–CaCl2, NdCl3–KCl, NdCl3–NaCl, and NdCl3–CaCl2 melts measured dilatometrically were represented by the empirical equations as functions of temperature. The molar volumes of the melts were calculated from the density data.
The Reactions of Cyclic Sulfilimines with Cyanide Ion and Phosphine: Evidence for Substitution on Trivalent Sulfur
Authors: Aida Tetsuo , Nakajima Masashi , Inoue Teruhiko , Furukawa Naomichi , Oae Shigeru
Published: July 2006

The effect of ring size on the reaction of N-p-tosylsulfilimine with such nucleophiles as CN− and n-Bu3P was investigated kinetically and compared with the effect on the reaction of the corresponding cyclic sulfonium salt. The results indicated that the SN2–S process is more probable than the SN2–N route.
Reaction of 1,3-Oxazinium Salt with Active Methylene Compounds
Authors: Shibuya Isao , Kurabayashi Masahiro
Published: July 2006

2,4,6-Triphenyl-1,3-oxazinium perchlorate reacts with active methylene compounds to give several butadiene derivatives and various pyridine derivatives. The reactions seem to proceed as follows: The carbanion from an active methylene compound attacks the 6-position of the oxazinium ring, and opens the ring to form a butadiene as an intermediate, which is then recyclized to a pyridine derivative according to a characteristic mode. The mode of recyclization differs with the constituent of each active methylene. There are five modes characteristic of cyano-, ester-, amido- and benzoyl constituents and nitromethane. A compound containing two different constituents usually follows either of the two possible modes.
Photoreaction of Bicyclo[5.3.0]dec-1(7)-en-2-one with Cyclopentene and Cyclohexene
Authors: Kunai Atsutak , Omori Takeshi , Kimura Koji , Odaira Yoshinobu
Published: July 2006

The photoreaction of the enone (I) with cyclopentene gave the radical coupling products, (VII) and (VIII), along with the hydrogen abstraction product (VI), but not [2π+2π] photocycloadduct. On the other hand, the photoreaction of I with cyclohexene proceeded in somewhat different manner to give the [2π+2π] photocycloadduct (V) other than the hydrogen abstraction product (VI) and the radical coupling product (IX).
Oxidation by Iron(III) Complexes. IX. The Preparation of α-Diketones by the Oxidation of Enolizable Ketones with the Iron(III) Chloride–Pyridine Complex under Oxygen
Authors: Inoue Hiroo , Hata Hiroyuki , Imoto Eiji
Published: July 2006

The oxidation of deoxybenzoin and p-substituted deoxybenzoins with an iron(III) chloride–pyridine complex under air or oxygen was investigated. The reaction afforded the corresponding α-diketones in a satisfactory yield.
The Synthesis and Polymerization of 2-(p-Vinylphenyl)-4,6-diamino-s-triazine
Authors: Oikawa Eizo , Horiguchi Kazuya
Published: July 2006

A new olefinic s-triazine, that cited in the title, was prepared by the reaction of p-cyanostyrene with dicyandiamide. Methyl p-vinylbenzoate could provide the triazine in an improved yield. The triazine readily underwent radical polymerization in an aprotic solvent to give a soluble and thermally stable polymer.
Syntheses and Ring Opening Reactions of 2-Alkyl-3,3-dichlorospiro-[cyclopropane-1,9′-fluorene] Derivativatives
Authors: Wada Eiji , Fujisaki Shizuo , Nagashima Akiko , Kajigaeshi Shoji
Published: July 2006

2-Alkyl-3,3-dichlorospiro[cyclopropane-1,9′-fluorene] derivatives (4) were obtained by the addition of CCl2 to 9-alkylidenefluorenes. Ring opening reactions of 4 with bases gave enynes, butadienes, or butatrienes.
Rate of the Dushman Reaction in Iodic Acid at Low Iodide Concentration. Complexity of Iodic Acid
Authors: Furuichi Ryusaburo , Liebhafsky Herman A
Published: July 2006

Three rate laws have been postulated for the Dushman reaction, 6H++5I−+IO3−=3H2O+3I2, with total reaction orders of four, five and six, at iodide ion concentrations below 10−8 M. New direct measurements of the rate and an examination of thermodynamic data for iodic acid solutions have eliminated some of the confusion. The complexity of iodic acid solutions, with and without added salt, makes it impossible to establish a single reaction order from the radioactive iodine exchange measurements. The new results are best expressed by a quasiempirical rate equation, −d[IO3−]⁄dt=8.59×104[H+]2(I−)[IO3−] mol l−1 min−1, which is closely approximated by −d[IO3−]⁄dt=γ±p4(H+)2(I−)(IO3−){k′+k″(HIO3)} mol l−1 min−1, with k′=2.83×105 mol−3 l3 min−1 and k″=6.60×106 mol−4 l4 min−1 for 25 °C. The second rate law is interpreted in terms of a reasonable mechanism that takes into account the thermodynamically established polymerization in iodic acid solutions.
The Reaction of Hydrogen Atoms with Acetylene
Authors: Ibuki Toshio , Takezaki Yoshimasa
Published: July 2006

The addition of hydrogen atoms to acetylene has been investigated at room temperature. The relative rate constant for

&H+C_2H_4→C_2H_5, \labeleq1

&H+C_2H_2→C_2H_3, \labeleq2

was found to be k1/k2=9.99±0.16. The ratios of the rate constant of disproportionation to that of the combination for the same radicals and for different radicals were determined to be as follows:

2C_2H_5+C_2H_3 &→1-C_4H_8, & & (4)

& →C_2H_6+C_2H_2, & & (4a)

& →2C_2H_4, & & (4b)

k_4a/k_4& =0.369,

k_4b/k_4& =0.68,

C_2H_3+C_2H_3& →1,3-C_4H_6, & & (5)

& →C_2H_4+C_2H_2, & & (5a)

k_5a/k_5& =0.087.
Nucleophilic Substitution on Trivalent Nitrogen Atom. Menschutkin Type Reaction of O-2,4-Dinitrophenylhydroxylamine with Uncharged Nucleophiles
Authors: Yamamoto Fumio , Oae Shigeru
Published: July 2006

Kinetic investigation carried out on the reaction between O-2,4-dinitrophenylhydroxylamine and neutral nucleophiles revealed that the reaction is a typical SN2 reaction on the trivalent nitrogen atom. Moreover, the order of reactivities of common nucleophiles was found to be somewhat similar to that of the nucleophilicities toward sp3 carbon atom. However, unlike the SN2 reaction on sp3 carbon atom, the SN2 reaction on the trivalent nitrogen atom found to be not very sensitive to the steric effect of substituted pyridine.
A Configuration Analysis of the Electronic States of Aniline
Authors: Suzuki Satoshi , Fujii Tsuneo
Published: July 2006

The method of configuration analysis has been applied to the interpretation of the ground and the excited electronic states of aniline. The results of full analysis, including all the singly and the doubly excited configurations, is presented. The electronic wave functions analyzed were obtained by a procedure of the Pariser-ParrPople type. The first excited singlet state of aniline is assigned to the 1Lb. The second, the third, and the fourth excited singlet state are assigned to the mixed state of the 1La and 1CTSl states, the 1CTA, 1Bb, and 1Lb states, and the 1Ba and 1La states respectively. The lowest triplet state of aniline is assigned to the 3La state. The total weights of all the singly excited configurations range from 88% to 95%, except for the ground state. The inclusion of all the doubly excited configurations improves the weights up to 99.6% or more.
Complexes between Nucleotide Base and Amino Acid. I. Crystal Structure of Cytosine: N-Formylglycine
Authors: Ohki Minoru , Takenaka Akio , Shimanouchi Hirotaka , Sasada Yoshio
Published: July 2006

Cytosine: N-formylglycine complex crystallizes in the space group Pna21 with cell dimensions of a=8.444(2), b=21.169(5), and c=5.120(1) Å. The structure was solved by the trial-and-error method on the basis of a Patterson map. A full-matrix least-squares refinement led to an R value of 0.035. The difference map revealed the protonation of cytosine by the carboxyl group of N-acylamino acid and the involvement of ionic interaction in complex formation. This mode is the same as proposed for cytosine: N-benzoylglycine complex in spite of different molecular environment. Such arrangement of cytosine and ionized carboxyl group of amino acid may suggest a mutual recognition scheme between nucleic acid and protein.
Thermal Dehydration and Decomposition of Dioxalato Complexes of Be(II), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) in Solid State
Authors: Nagase Kenzo , Sato Katsuya , Tanaka Nobuyuki
Published: July 2006

The structures of anhydrous dioxalato complexes K2[M(C2O4)2] (M: Mn(II), Co(II), Ni(II), Cu(II), and Zn(II)) prepared by heating their hydrates, were examined by means of infrared absorption and visible reflectance spectroscopy. It was found that the anhydrous complexes of Mn(II), Co(II), and Zn(II) exist in a polynuclear octahedral form with a bridging oxalate group, and those of Ni(II) and Cu(II), in a monomer form. On further heating, the complexes of Be(II), Mn(II), and Zn(II) decomposed into the corresponding metal oxides and potassium oxalate, and those of Co(II), Ni(II), and Cu(II) into the corresponding metals and potassium oxalate. Except for the beryllium(II) complex, the complexes decomposed at lower temperatures with an increase in 1/r, where r is the radius of metal ion.
Thermal Products in the System of NaPO3 Glass-Al2O3
Authors: Watanabe Makoto , Sato Shoji , Saito Hajime
Published: July 2006

The glassy and crystalline products were made by heating a mixture of aluminum oxide and sodium metaphosphate glass with P/Al ratios in the range from 1.0 to 300 at 1000 °C for 3 hr. The crystalline substance was present in the products with P/Al ratios smaller than 5.0 and was, except for aluminum oxide, always aluminum orthophosphate. The quantitative analysis and the measurement of the average chain length of the phosphates contained in the soluble parts of the products showed that aluminum oxide reacts with sodium metaphosphate to make Al–O–P linkages. A theoretical treatment of the average chain length of the polyphosphates present in the aluminate-phosphates was also made. By comparing the calculated average chain length with the measured one, it has been concluded that the most reasonable chemical structure of the glassy products of the aluminate-phosphates is Al(OP)3. By the analysis of the infrared spectra of the thermal products, four-way branching points may be said to exist in the glassy products.
Preparation of cis- and trans-Dicyanobis(ethylenediamine)chromium(III) Complexes and Optical Resolution of the cis Isomer
Authors: Kaizaki Sumio , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Two geometrical isomers, cis and trans, of [Cr(CN)2(en)2]+ were prepared and the cis isomer was resolved into optical isomers. The ligand field absorption and circular dichroism spectra were discussed and the absolute configuration of cis-(+)546-[Cr(CN)2(en)2]+ was determined to Λ on the basis of the circular dichroism sign in the first spin-allowed d-d band region.
Resins from Formaldehyde. 103. Reaction of Naphthalene with Aqueous Formaldehyde Solution
Authors: Ouchi Tatsuro , Otsuka Saburo , Imoto Minoru
Published: July 2006

The reaction of naphthalene(N) with formaldehyde(F) was carried out in dioxane or an acetic acid/water solution, using sulfuric acid as the catalyst. The rate of the consumption of F is proportional to [N]1.12[F]1.05-[H2SO4]1.05. The activation energies and entropies of the reaction of N, α- and β-naphthyl carbinol(NC) with F were estimated to be 21.4, 15.3, and 16.0 kcal/mol and −19.1, −36.2, and −33.2 e.u., respectively. The reaction products were isolated and their structures were identified as α-NC, αα′-, αβ′-dinaphthylmethane, three-and four-nuclear compounds, which are linked to each other with methylene or methylene ether bonds at the α- or β-positions; identified was done by means of the IR, NMR, and UV spectra, molecular-weight measurements, elemental analysis, and thin-layer chromatography. In addition to the compounds described above, acetyl esters were obtained when the reaction was carried out in the presence of acetic acid. The reactivities of the α-position of N and its derivatives was larger than those of the β-position. Moreover, the resin formation from N and F was studied by means of gel-permeation chromatography. On the bases of these results, the reaction route of N with F to resin was deduced.
Studies of the cis-trans Isomerization of 3-Aryl-1,2,3-oxathiazolidine-2-oxides
Authors: Nishiyama Tomihiro , Yamada Fukiko
Published: July 2006

The isomerization of the cis- or trans-3-aryl-1,2,3-oxathiazolidine-2-oxides was investigated under various conditions. The isomerization proceeded in carbon tetrachloride, chloroform, and benzyl chloride solutions at a low temperature. On the other hand, in other organic solvents, such as benzene, acetone, pyridine, N,N-dimethylformamide, and chlorobenzene, isomerization did not occur. The results can be explained by the mechanism which yields the open-chain halosulfamic acid anion by the attack of a halogen ion on the 5-position. The anion can close to cis- or trans-oxathiazolidine.
Effect of Solvent Viscosity on the Decomposition of 1,1,4,4-Tetraphenyl-2-tetrazene
Authors: Sugiyama Kazuo , Nakaya Tadao , Imoto Minoru
Published: July 2006

The rate of decomposition of 1,1,4,4-tetraphenyl-2-tetrazene (TPT) was measured in the polyethylene glycol (PEG) thickened dimethylformamide (DMF) of varying viscosities. The observed rate constant for the decomposition of TPT decreases with the viscosity of the DMF/PEG solvent system. A compensating change was found in the enthalpy and entropy of activation. It was also found that the decomposition of TPT occurs by the scission of only one N–N single bond, and undergoes cage return in the solvent system by recombination of radicals.
The Synthesis of Heterocyclic Compounds by the Reaction of Tin(II) Bis(acetylacetonate) with Isocyanates
Authors: Wakeshima Ikuko , Kijima Ichiro
Published: July 2006

It was found that phenyl isocyanate reacted with tin(II) bis(acetylacetonate) to yield triphenyl isocyanurate, 5-acetyl-6-methyl-2-oxo-3-phenyl-4-phenylimino-3,4-dihydro-2H-1,3-oxazine, and N,N′-diphenylurea, while ethyl isocyanate reacted with tin(II) bis(acetylaceonate) to afford only 2,4-dioxo-6-ethylimino-1,3,5-triethylhexahydro-1,3,5-triazine.
Studies of Saturated Heterocyclic Compounds. II. The Preparation and PMR Spectroscopic Study of Mono- and Di-substituted-1,3-dioxolan-4-ones
Authors: Asabe Yoshihiro , Takitani Shoji , Tsuzuki Yojiro
Published: July 2006

The relationship of the configurations and the magnitude of the long-range spin coupling constants between the 2-H and 5-H, J2,5, of 1,3-dioxolan-4-ones has been elucidated, the J2,5(trans) value being always larger than the J2,5(cis) value. Geometrical isomers of several 2,5-disubstituted derivatives have been separated by means of preparative tlc and assigned by means of PMR spectroscopy, especially by the use of their J2,5 values. The sign of the J2,5, values for a 2-trichloromethyl derivative has been determined by a partial decoupling experiment, both J2,5(cis) and J2,5, (trans) being positive.
Nuclear Magnetic Resonance Studies of Bicyclic Thiophene Derivatives. II. Through Space H–F Coupling in o-Fluorophenyl Derivatives of Benzoylthiophene, Thienopyrimidine and Thienodiazepine Derivatives
Authors: Hirohashi Toshiyuki , Inaba Shigeho , Yamamoto Hisao
Published: July 2006

Proton–fluorine coupling over six bonds has been observed between fluorine and Hβ of the thiophene ring in ortho fluorophenyl derivatives of 4-phenylthienopyrimidines (1), 2-acetylamino-3-benzoylthiophenes (2), 5-phenyl-1,4-thienodiazepines (3) and 5-phenyl-1,4-thienodiazepine-4-oxides (4). The solvent effect and the N-methylation effect on the coupling constant can be explained by considering that the H–F coupling is a through space coupling. The value of coupling constant (JHF: 0.5 Hz to 4.1 Hz) depends upon the geometry of the ring system condensed at 2-C and 3-C of thiophene ring, decreasing in the order of 1>2>3>4. A discussion is given on the manner of steric repulsion between the benzene ring and some atoms on the other moiety of these compounds.
CNDO/2 Calculations of the Ionization Potentials and Electronic Spectra of Some Unsaturated Hydrocarbons
Authors: Hayashi Toshio , Nakajima Takeshi
Published: July 2006

A modified CNDO/2 method in which local core matrix elements are taken to be empirical parameters is presented. Using this method, the ionization potentials and electronic spectra of some unsatutated hydrocarbons, ethylene, trans-, cis-1,3-butadienes, cyclobutene, cyclopentadiene, benzene and naphthalene, were calculated. The results are in general agreement with the previously available experimental information.
Some Mixed-Ligand Iron(III) Complexes Produced by Reactions of Tris(acetylacetonato)iron(III) with Hydrogen Halides in Organic Solvents
Authors: Takeda Kenji , Isobe Kiyoshi , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

Tris(acetylacetonato)iron(III) Fe(acac)3 reacts with an equimolar and double molar amounts of a hydrogen halide in dichloromethane to afford the mixed-ligand iron(III) complexes, FeX(acac)2 and FeX2(acac)H2O, respectively, where X is Cl or Br. They are all high-spin iron(III) complexes and exist as monomeric five-coordinate molecules in non-coordinating solvents, but behave as uni-univalent electrolytes in methanol. Further reactions of FeX2(acac)H2O with an excess of hydrogen halides in dichloromethane followed by the addition of twice as many moles of 1,10-phenanthroline produced [FeX2(phen)2]X. The reactions of FeX2(acac)H2O with excesses of pyridine and 2,2′-bipyridine in tetrahydrofuran gave the six-coordinate complexes FeX2(acac)(py)2and FeX2(acac)(bipy), respectively.
Diprotonated Bimetallic Complex between Copper(II) with 3,3′-Bis[N,N-bis(carboxymethyl)aminomethyl]-o-cresolsulfonphthalein
Authors: Yamada Mutsuo
Published: July 2006

The solution chemistry for complexes of copper(II) with 3,3′-bis[N,N-bis(carboxymethyl)aminomethyl]-o-cresolsulfonphthalein(XO) is studied by spectrophotometric measurement. Copper(II) is found to form a diprotonated bimetallic complex with XO in weakly acidic medium. Stability constant and molar absorptivity of the complex are evaluated to be logKCu2LH2=9.86±0.05 and ε574nm=3.73×104 M−1 cm−1, respectively, at 25.0 °C and I=0.1 M. Thermodynamic parameters are calculated to be ΔH=4.3 kcal·mol−1 and ΔS=64 eu at 25.0 °C and I=0.1 M.
Derivatographic Studies on Transition Metal Complexes. XVII. Solid-phase Deaquation-anation of Some Optically Active Aqua—cobalt(III) Complexes
Authors: Tsughiya Ryokichi , Omote Masakatsu , Uehara Akira , Kyuno Eishin
Published: July 2006

Stereochemical changes involved in the solid-phase deaquation-anation of the following optically active aqua-cobalt(III) complexes were investigated: (+)546-cis-[Co(H2O)2en2]X3·2H2O (X=Cl or Br), (+)589-cis-α[CoCl(H2O)en2]Cla·H2O, (−)589-cis-[CoCl(H2O)en2]Br2·H2O, (+)589-α-[CoCl(H2O)trien]Cl2·H2O and (+)589-α-[CoCl(H2O)trien]Br2·2H2O, where en and trien denote ethylenediamine and triethylenetetramine, respectively. Thermal deaquation-anation processes for each complex were observed with a derivatograph, polarimeter, and UV and CD spectrophotometers. cis-[Co(H2O)2en2]Cl3·2H2O was converted into cis-[CoCl(H2O)en2]Cl2 at first and then cis-[CoCl2en2]Cl; the stereochemical changes during the first step and the second step were found to be retention and racemization, respectively. In contrast, a predominant stereochemical change involved in the deaquation-anation of cis-[Co(H20)2en2]Br3·2H2O was cis-to-trans isomerization. The deaquation-anation of cis-[CoCl(H2O)en2]Cl2·H2O and cis-[CoCl(H2O)en2]Br2·2H2O was found to be accompanied by racemization and by greater parts of cis-to-trans isomerization, respectively. However, both α-[CoCl(H2O)trien]Cl2·H2O and α-[CoCl(H2O)trien]Br2·2H2O undergo deaquation-anation with retention.
A Convenient Synthesis of β-Acetyl-γ-substituted-γ-butyrolactones and γ-Acetyl-δ-substituted-δ-valerolactones
Authors: Sato Toshio , Hanna Junichi , Nakamura Hideo , Mukaiyama Teruaki
Published: July 2006

A convenient method for the preparation of β-acetyl-γ-substituted-γ-butyrolactones (III) and γ-acetyl-δ-substituted-δ-valerolactones (IV) is described. It was established that α-angelicalactone (I) and 3,4-dihydro-6-methyl-2H-pyran-2-one(II) react with various aldehydes in the presence of boron trifluoride etherate (BF3·OEt2) to afford the corresponding γ and δ-lactones, respectively, in good yields.
Hydrolysis of Carbohydrates in the Presence of a Reversed Micelle. I. Hydrolysis of Sucrose in a Dioxane–Water Mixed Solvent
Authors: Arai Kenichiro , Ogiwara Yoshitaka , Ebe Kazuyoshi
Published: July 2006

Formation of a reversed micelle by dodecybenzenesulfonic acid (DBSH) in a dioxane–water mixed solvent was discussed in terms of the behavior of critical micelle concentration and NMR study. Hydrolysis of sucrose in the presence of the reversed micelle was then investigated. The pseudo-first-order rate constant of the reaction showed a tendency to increase with decreasing substrate concentration and increasing dioxane composition, and the maximum rate acceleration obtained in the present experiment was 21-fold on the basis of the reaction in aqueous solution. The rate acceleration may result from the solvent effect of dioxane relating to the structuredness of water and the substrate binding effect due to the formation of the reversed micelle.
Studies of Unusual Amino Acids and Their Peptides. VI. The Syntheses and the Optical Resolutions of β-Methylphenylalanine and Its Dipeptide Present in Bottromycin
Authors: Kataoka Yoshiharu , Seto Yasuhiko , Yamamoto Masaaki , Yamada Takashi , Kuwata Shigeru , Watanabe Hiroshi
Published: July 2006

β-Methyl-phenylalanine was prepared by the condensation of α-methylbenzyl bromide with acetaminomalonate, followed by the hydrolysis and decarboxylation of the condensate. The decarboxylation occurred diastereoselectively to some extent. The erythro and the threo isomers could be separated by the fractional crystallization of their benzoyl derivatives, and differentiated by means of their NMR spectra. The optical resolution of the respective isomers was attained by treating the benzyloxycarbonyl derivatives with qunine or quinidine; thus, the four isomers could be obtained in a pure state. A dipeptide present in the C-terminal of bottromycin was synthesized by coupling N-protected erythro-l-β-methyl-phenylalanine with either l-β-(2-thiazolyl)-β-alanine ester or, more conveniently, with the Dl-compound, and by separating thereafter.
Bromination and Mercuration of Bis-dimethlglyoximato(1-octenyl)-pyridinecobalt(III), 1-Octenyl Cobaloxime
Authors: Tada Masaru , Kubota Minoru , Shinozaki Hiraku
Published: July 2006

cis-1-Octenyl(pyridine)cobaloxime (I) and trans-1-octenyl(pyridine)cobaloxime (II) were prepared by the reaction of cobaloxime anion with cis-and trans-1-halooctene, respectively. Bromination of I and II in polar solvents gave preferentially cis  trans-1-bromooctene. Bromination of I in carbon disulfide also gave preferentially trans-1-bromooctene, but bromination of II gave more cis-1-bromooctene. Mercuration of I and II with mercuric acetate in DMF gave preferentially 1-octenylmercury(II) compound with retention of configuration, but the mercuration in acetic acid gave ca. 1 : 2 mixture of cis and trans-1-octenylmercury(II) compound. Two mechanisms are proposed for these electrophilic displacement reactions; one involves the addition of electrophile as a first step, followed by the elimination of cobaloxime moiety, and the other involves the addition of bromonium or mercury(II) ion, followed by the elimination of cobaloxime moiety.
A Convenient Synthesis of Indolotropones and 6-Substituted 5-Azabenz[b]azulenes
Authors: Yamane Kameji , Fujimori Kunihide
Published: July 2006

Several substituted indolo[2,3-b]tropones were prepared by the dehydrobromination of 7,7-dibromo-7,8,9,10-tetrahydrocyclohept[b]indole-6(5H)-ones (2a–h), which had been obtained by the bromination of 7,8,9,10-tetrahydrocyclohept[b]indol-6(5H)-ones (1a–h) with phenvltrimethylammonium tribromide (PTAB). 6,7,8,9-Tetrahydrocyclohept[b]indole-10(5H)-one (5a) and 6,7,8,9-tetrahydro-5-methylcyclohept[b]indol-10(5H)-one (5b) were obtained by the oxidation of hexahydrocyclohept[b]indole (4a) and the 5-methyl derivative (4b) with dichlorodicyanobenzoquinone (DDQ). Indolo[3,2-b]tropones (6a and 6b) were derived from 5a and 5b respectively. The reactions of 6-chloro-5-azabenz[b]azulene (8) with nucleophilic reagents gave the corresponding substituted products (9a–j).
The Reaction of Anhydrochloralurethanes with Ketene Acetals
Authors: Akiyama Tetsuo , Urasato Nobuaki , Imagawa Takeshi , Kawanisi Mituyosi
Published: July 2006

The reaction of anhydrochloralurethanes (I) with ketene acetals (II) has been found to give novel carbamate derivatives (III) in quantitative yield. The intermediacy of a cyclic intermediate, an oxazine derivative (IV), was confirmed by spectroscopic methods, although several attempts to isolate IV have been unsuccessful. The mechanism for formation of IV is discussed.
The Electrochemical Fluorination of Trifluoromethyl-substituted Benzenes
Authors: Yonekura Michimasa , Nagase Shunji , Baba Hajime , Kodaira Kazuo , Abe Takashi
Published: July 2006

The electrochemical fluorination of benzenes containing one or two trifluoromethyl groups has been carried out. They afforded perfluorocyclohexane derivatives with the trifluoromethyl group in good yields. Chlorobenzenes containing a trifluoromethyl group yielded chlorinecontaining perfluorocyclohexane derivatives carrying the trifluoromethyl group. Trifluoromethylbenzonitriles gave perfluoro(dimethylcyclohexane)s, whereupon the nitrile group was converted into a trifluoromethyl group, thus releasing nitrogen trifluoride. The electrochemical fluorination of a trifluoromethylnaphthalene gave perfluoro(methyldecahydronaphthalene) only in a small yield.
Catalytic Reduction of Sulfoxide by Bromine-Hydrogen Bromide System
Authors: Aida Tetsuo , Akasaka Takeshi , Furukawa Naomichi , Oae Shigeru
Published: July 2006

A small amount of hydrogen halides or halogens was found to catalyze the decomposition of dimethyl sulfoxide (DMSO), affording dimethyl sulfide (DMS) and other oxidized products. Of the halides or halogens, either bromine or hydrogen bromide is the most effective. DMSO decomposes until it is completely consumed. This catalytic decomposition takes place with other sulfoxides such as diethyl or tetramethylene sulfoxide but sluggishly with alkyl aryl or diaryl sulfoxides. The reaction with bromine apparently proceeds via the initial α-bromination of DMSO to afford α-bromomethyl methyl sulfoxide which is oxidized by (Kornblum Reaction) to afford such products as formaldehyde, methanesulfonic acid, and hydrogen bromide. These consecutive reactions form a process of “Oxidation-Reduction Cycle” between bromine-hydrogen bromide and DMSO-DMS. The effects of salts and DMS on the rate of decomposition are discussed.
Backbone Rearrangements of 3α,4α-Epoxyshionane into Bacchar-12-en-3α-ol and D: B-Friedo-bacchar-5(10)-en-3α-ol
Authors: Yamada Shûzô , Yamada Sachiko , Tachibana Kazuo , Moriyama Yoshihiko , Tanahashi Yoshiaki , Tsuyuki Takahiko , Takahashi Takeyoshi
Published: July 2006

Upon treatment with boron trifluoride etherate, 3α,4α-epoxyshionane (7) rearranged into bacchar-12-en-3α-ol (9) and D : B-friedo-bacchar-5(10)-en-3α-ol (10), and their structures have been determined. Revision of the structure for the latter product from previously reported D : C-friedo-bacchar-8-en-3α-ol (20) to 10 was described.
Oxidation of 4-Alkyl-1-hydroxyimino-2,4,6-tri-t-butyl-2,5-cyclohexadienes : Formation of 4-Alkyl-2,6-di-t-butylnitrobenzenes via Iminoxyl Radical
Authors: Inagaki Yoshio , Okazaki Renji , Inamoto Naoki
Published: July 2006

Reactions of 4-alkyl-1-hydroxyimino-2,4,6-tri-t-butyl-2,5-cyclohexadienes (1) with silver(I) oxide afforded 4-alkyl-2,6-di-t-butylnitrobenzenes (2) mainly, which were found to be formed via an iminoxyl radical on the base of the ESR spectra and by-products, 4-alkyl-1-t-butoxyimino-2,4,6-tri-t-butyl-2,5-cyclohexadienes (3). This reaction is a novel oxidative decomposition of iminoxyl radical and provides a practical preparative method for the nitrobenzenes (2). Oxidation of 1 with other reagents (nickel peroxide and m-chloroperbenzoic acid) and oxidation of 6-alkyl-1-hydroxyimino-2,4,6-tri-t-butyl-2,4-cyclohexadienes (5) have also been described.
Vapor-Phase Photolysis of cis-Cyclononene
Authors: Inoue Yoshihisa , Takamuku Setsuo , Sakurai Hiroshi
Published: July 2006

Direct and sensitized photolyses of cis-cyclononene (1c) vapor were investigated. The direct irradiation of 1c gave 1,8-nonadiene(2) and vinylcycloheptane via the thermally-activated ground state produced by rapid internal conversion from the excited singlet state initially generated. On the other hand, the sensitized photolysis of 1c gave 2 and five bicyclononanes, which are interpreted in terms of intramolecular hydrogen transfer reactions.
Syntheses of 3,4-Dimethylpyrrole
Authors: Ichimura Kunihiro , Ichikawa Susumu , Imamura Kazuo
Published: July 2006

Treatment of N-sulfinyl compound with 2,3-dimethylbutadiene gives a cycloadduct which affords 3,4-dimethylpyrrole in satisfactory yields by heating in a strongly alkaline methanolic solution.
A Synthesis of Methyl 2-Dimethylphosphoenolpyruvate by Dephosphorylation
Authors: Watanabe Kugako , (Kato) Ishimatsu Michiko , Tasaka Koa
Published: July 2006

Methyl 2-dimethylphosphoenolpyruvate was obtained by base-catalyzed dephosphorylation of methyl 2,3-bis(dimethylphospho)glycerate.
NMR Spectroscopic Studies on the Tautomerism in Schiff Bases of Tenuazonic Acid Analogs
Authors: Yamaguchi Tatsuaki , Saito Kimitoshi , Tsujimoto Toshio , Yuki Hidetaka
Published: July 2006

A NMR spectroscopic study of 15N-enriched Schiff bases of such tenuazonic acid analogs as 3-acetyltetramic acid, 3-acetyltetronic acid, and 3-acetylthiotetronic acid showed the predominance of ketamine forms in their tautomeric equilibria in CDCl3. The ratios of “external tautomers” between two different ketamine forms, as calculated from the 15N–H signal intensities, were compared favorably with the ratios obtained from the ring methylene signals.
Electronic Structure of Porphyrins. I. SCF-MO-CI Calculation Based on π-Electron Approximation
Authors: Tomono Kotaro , Nishimoto Kichisuke
Published: July 2006

The electronic structure and electronic spectra of metal free and metal porphyrins have been investigated by the MO method. In order to elucidate the effect of electron correlation on the electronic transitions, a new approximation for electron repulsion integral has been examined. For metal free porphyrin, the effect of hydrogen bondings on the electronic transitions has also been investigated. In metal porphyrin, the present calculation showed that almost two units of charges are transferred from the ligand porphyrin to the central metal ion through σ-type co-ordination bond. A satisfactory agreement between the calculated results and the experimental data was obtained when a new expression for electron repulsion integral, in which the effect of electron correlation is considered, was used. It was found that the Soret band of metal free porphyrin consists of almost degenerated Bx and By species.
X-Ray Photoelectron Spectra of Aryl-nickel Complexes
Authors: Sen\={o} Manabu , Tsuchiya Shinji , Hidai Masanobu , Uchida Yasuzo
Published: July 2006

The nature of bondings in aryl-nickel complexes has been clarified by means of X-ray photoelectron spectroscopy (XPS). Pi bonding between nickel and aryl ligand seem to be of little importance. Ni–Cl bondings are of partially ionic character. A correlation between stereochemical structure and satellites has been discussed. It is suggested that the aryl-nickel complexes examined have diamagnetic square-planar structures. Measurements of solid-state susceptibilities support this view.
An X-Ray Study of Non-stoichiometric Pr0.6Gd0.4O1.5+δ
Authors: Endo Kazuhiro , Yamauchi Shigeru , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

Non-stoichiometric Pr0.6Gd0.4O1.5+δ (δ=0.000, 0.075, 0.120, and 0.157), with a bixbyite structure, was investigated by X-ray diffraction. The intensities of the superlattice lines were found to decrease with an increase in δ. The structure analysis has revealed that metal ions gradually move to the ideal positions of the fluorite structure with an increase in δ and that excess oxygen ions preferentially occupy the Z-sites.
ENDOR Studies of the Hindered Internal Rotation of Alkyl Groups in the 1,4-Dialkyl Naphthalene Radical Anions
Authors: Nemoto Fujito
Published: July 2006

The ENDOR spectra were measured for the anion radicals of 1,4-dimethylnaphthalene, 1,4-diethylnaphthalene, and 1,4-dipropylnaphthalene. The β-proton splittings of the alkyl groups were 3.30, 2.85, and 2.44 G at −80 °C for 1,4-dimethyl-, 1,4-diethyl-, and 1,4-dipropylnaphthalene respectively, and the positive temperature dependence of the β-proton splitting was demonstrated. Based on the Heller-McConnell relationship, a1,4β=(B0+B2cos2θ)ρ1.4π the β-proton splittings and their temperature dependence were interpreted in terms of a modified model of the restricted internal rotation of ethyl and propyl groups over two kinds of potential barriers. The rotational potential barriers thus estimated were 3.0 and 0.7 kcal/mol for the 1,4-diethylnaphthalene anion and 6.0 and 1.2 kcal/mol for the 1,4-dipropylnaphthalene anion. In the ENDOR spectra of potassium 1,4-diethylnaphthalene observed in THF solutions, two ENDOR lines attributed to the non-equivalent alkyl β-protons were observed at −110 °C, these lines collapsed to a single line when the temperature was raised to −70 °C. This phenomenon can be understood on the assumption that the steric effect of the solvated cation alters the rotational potential curve from a symmetric to an asymmetric one.
The Tribosorption of Hydrogen to Silicon Carbide
Authors: Ichioka Koji , Ito Tomoyasu , Shirakawa Toshiaki , Toi Keio , Tokuda Taneki
Published: July 2006

The tribosorption of hydrogen into granular silicon carbide was studied under shaking in the pressure range of 0.04–1 Torr at room temperature. The sorption was observed when the frequencies of the vibration were 10.0 and 13.3 Hz, but was not observed when they were 0 and 6.7 Hz. The rate of tribosorption evaluated from the change in the pressure of gas had its maximum value when the sample was shaken for 20–40 h. It was found that this tribosorption could be attributed to an absorption to the solid and could be treated as a diffusion process. The time dependence of the diffusion coefficient showed a behavior similar to that of the lattice defect. It is suggested that the chemical properties of hydrogen and the activation of the solid play important roles in the tribosorption process.
Magnetic Properties of [(H2O)2M{(OH)2Coen2}2](X)2·nH2O (M=Ni or Co, X=SO4 or S2O6 and n=5 or 7)
Authors: Kobayashi Hanako , Ohki Kazuo , Tsujikawa Ikuji , Osaki Keiji , Uryû Norikiyo
Published: July 2006

The magnetic properties of [(H2O)2Ni{(OH)2Coen2}2](SO4)2·7H2O, [(H2O)2Co{(OH)2Coen2}2](SO4)2·5H2O, [(H2O)2Co{(OH)2Coen2}2](SO4)2·7H2O, and [(H2O)2Co{(OH)2Coen2}2](S2O6)2·5H2O were investigated on powder samples. The paramagnetism of these compounds was considered to be that of the central Ni2+ or Co2+ion. From the fits of the experimental data with the calculated magnetic susceptibilities and the simulations of the ESR derivative curves, the ligand field parameters and g-values were determined. The ligand field around the Co2+ ion in [(H2O)2Co{(OH)2Coen2}2](SO4)2·5H2O was concluded to be tetragonal and in the other samples the ligand fields at the central divalent ions were found to be rhombic.
Degradation Spectra and the G-values for Ionization and Excitation of the Mixtures of Noble Gases
Authors: Okazaki Kiyoshi , Oku Eizo , Sato Shin
Published: July 2006

Degradation spectra of electrons and the W-values in the mixtures of He–Ne, He–Ar, Ne–Ar, and Ne–Kr irradiated by 100 keV electrons have been calculated by using the binary-encounter theory and the theory of the degradation spectrum. On the basis of these calculations, the Jesse effect, the negative Jesse effect, and the non-metastable Penning effect have been reconsidered. It was shown that at least a part of the negative Jesse effect and the non-metastable Penning effect are explicable as due to the degradation spectra of electrons.