bluuebunny/crossref_metadata_2025 huggingface dataset:
Infrared Intensities of Sodium, Calcium, and Potassium Hydroxide Crystals
Authors: Kamisuki Toshio , Maeda Shiro
Published: July 2006

The absolute intensities of OH− and OD− stretching absorptions in Na, Ca, and K hydroxide crystals have been measured in the films formed on a quartz window. The thickness of the films was determined by chemical or flame photometric analysis of the solution in which the sample film had been dissolved. The expected difference between OH− and OD− in the dipole-moment derivative, (dμ/dr)OD–(dμ/dr)OH, was observed to be in excellent or moderate agreement with the theoretical value given from Ellison’s equation for Na and Ca. This result also proves that the polarization of dμ/dr is in the O−–H+(D+) direction in these cases. As for K hydroxides, although the numeric results are rather dubious, the intensities are apparently by far greater than the two others, confirming the hydrogen-bond formation in this crystals, as suggested by the crystal structure and vibrational frequencies.
On the Electron-transfer Reaction Rate between Different Molecular Species of Aromatic Hydrocarbons as Measured by ESR
Authors: Suga Kosaku , Aoyagui Shigeru
Published: July 2006

The rate constants of electron-transfer reactions between the anthracene anion radical and pyrene, and those between the former radical and 1,2-benzanthracene, were measured by the ESR method in tetrahydrofuran containing 20 mm of tetra-n-butylammonium perchlorate. In the analysis of the experimental results, correction of the ESR line width was made for the change in the radical concentration caused by the addition of neutral molecules. The rate constants thus obtained were (2.0±0.4)×107m−1sec−1 and (8.1±1.0)×10−7m−1sec−1 respectively at 25°C. Under the same experimental conditions, the rate constants of the electron exchange of anthracene and pyrene with their respective anions were about one-tenth of the rate constants of free anions. This fact led us to the supposition that the anion radicals had been combined with tetra-n-butylammonium ions into stable ion-pairs in our experiment. A semi-empirical method was proposed for the theoretical calculation of the rate constant according to the theory of R. A. Marcus. The agreement of the observed and the calculated rate constants was satisfactory. Further discussion of the dependence of the rate constant on the standard free energy of reaction was made in connection with the so-called “Linear Free Energy Relationship.”
On the Long-range Interactions between Two Hydrogen Atoms and Two Helium Atoms
Authors: Yamabe Tokio , Ishimaru Shingo , Fukui Kenichi
Published: July 2006

The numerical results of the interaction energy between two hydrogen atoms and two helium atoms are examined with the use of exact formulae of the second-order perturbation energy using the Unsöld approximation. It is found that the analytic expression gives a good long-range interaction energy between two hydrogen atoms comparable to the best variational results so far obtained. In the case of two helium atoms, the result lies in between experimental data for large nuclear distances; this seems to support the reliability of the present estimation. Finally, the effectiveness of the Unsöld approximation is remarked on.
The Behavior of Indium(III) Complexes in Several Distribution Systems. II. The Extraction of Indium(III) Halide and Thiocyanate Complexes into 4-Methyl-2-Pentanone, 4-Methyl-2-Pentanol, or Nitrobenzene
Authors: Hasegawa Yuko , Takeuchi Hiroshi , Sekine Tatsuya
Published: July 2006

The solvent extraction of indium(III) from a bromide, iodide, or thiocyanate solution into 4-methyl-2-pentanone(MIBK), 4-methyl-2-pentanol(hexol), or nitrobenzene was determined by using a 114mIn tracer. The extraction was, in general, most effective with MIBK and poorest with nitrobenzene, except from iodide solutions. The extraction with a certain solvent was always better from iodide solutions than from bromide solutions. The extraction from thiocyanate solutions was better than that from iodide solutions in some cases, but it was poorer in other cases, and it was better than that from bromide solutions except with nitrobenzene. Furthermore, it was found that the distribution ratio, determined as a function of the ligand concentration, was always poorer when the aqueous phase contained only the sodium salt of these ligands than when it was 4m Na(X, ClO4) (where X denotes the ligand anion). The extractions from 4m Na(X, C1O4) were analyzed by using the stability constants for the indium complexes with these ligands in the aqueous phase, and the extraction equilibria were determined. From these results, it was concluded that these polar solvents extract not only the uncharged complex, InX3, but also the cationic and/or anionic indium complexes as ion-pairs, with the oppositely charged ions in the background salt, and that, in some cases, the solvent extracts only charged indium species. Thus, the difference in the distribution ratio in the presence and in the absence of the background sodium perchlorate was concluded to be caused not only by the change in the activities due to the change in the total salt concentration, but also by the extraction of ion-pairs of charged indium(III) species, which should be very much enhanced by the presence of the bulk perchlorate.
Polarographic Catalytic Waves of Titanium(IV) Chelates of EDTA and Related Compounds
Authors: Kaneko Hiroko , Ozawa Takeo
Published: July 2006

In the presence of the chlorate ion, the electrode reaction of the various titanium(IV)-chelates is followed by a cyclic process, i.e., an electrochemical reduction of electroactive species generated continuously by coupled chemical oxidation. The reaction rate constant of the regeneration is determined from the ratio of the limiting current observed by the DC polarographic method in the presence of the chlorate ion to that determined without it, and it is calculated using Koutecky’s equation. The complex-forming agent decreases the wave height of the catalytic waves of titanium(IV) chelates, and a clear dependency of the height of the catalytic waves on the dissociation constants of the titanium chelates is found. The catalytic wave heights of the titanium(IV) chelates decrease in the order of oxalic acid, NTA, EDTA-OH, EDTA, and CyDTA; the dependency on the stability seems to be the reverse. The logarithm of the dissociation constant is in a linear relation with the logarithm of the catalytic current. The mechanism is discussed on the basis of the above-mentioned facts.
Spectrophotometric Study on The Extraction of The Ternary Complex Composed of Cobalt(II), 8-Hydroxyquinoline-5-sulphonic Acid and Zephiramine
Authors: Kambara Tomihito , Sugawara Masao
Published: July 2006

8-Hydroxyquinoline-5-sulphonic acid (H2QS) reacts with cobalt(II) in the presence of zephiramine (tetra-decyl-dimethyl-benzyl-ammonium chloride) and gives a yellow green association complex. The ternary complex having an absorption maximum at 405 nm can be extracted into chloroform at pH 6.8–9.3. Beer’s law holds for 2.73–33.0 μg of cobalt(II); molar absorptivity, 1.39×104 cm−1mol−1l. The composition of cobalt(II)-H2QS complexes in water is 1 : 1 at pH 4.4, 1 : 2 at pH 5.8, and 1 : 3 at pH 7.6. The composition of the ternary complex is estimated to be [Co2+(QS2−)2(HQS−)(Z+)3]o. The equilibrium constant for the extraction

K=\frac[Co2+(QS2−)2(HQS−)(Z+)3]o[Co2+][(HQS−Z+)]o3[OH−]2

was determined. It was found that logK=29.01±1.86.
The Reaction and Reaction Products of μ-O2-Dicobalt Ammine Complexes with Nitrites, Thiocyanates, etc.
Authors: Shibahara Takashi , Mori Masayasu
Published: July 2006

In a neutral solution [NH3(en)2CoO2Co(en)2NH3]4+ was found to react with NO2− and SCN− to give [NO2-(en)2CoO2Co(en)2NO2]2+ and [SCN(en)2CoO2Co(en)2NCS]2+ respectively, without causing any cleavage of the O2-bridge, while in an acid solution it was found to be oxidized by NO2− to a μ-superoxo (O2−) complex ion, [NH3-(en)2CoO2Co(en)2NH3]5+. The latter is not affected by NO2−, in contrast with [(en)2Co(μ-NH2,O2)Co(en)2]4+, in which the O2−-bridge is replaced by an NO2−-bridge. The [NO2(en)2CoO2Co(en)2NO2]2+ formed as described reacts with CN− to give [Co2(CN)6(en)2O2]2−. The EPR spectra of some new μ-superoxo complexes which were synthesized by oxidizing some of the above μ-peroxo complexes were measured and compared with those of similar complexes. Infrared and electronic spectra were also taken.
Intramolecular Hydrogen Bonding in α-Keto and α-Alkoxy Carboxylic Acids. VIII. o-Methoxy-Substituted Phenoxyacetic and Phenylthioacetic Acids
Authors: Hirota Minoru , Hirano Go
Published: July 2006

The infrared spectra in the O–H stretching region of several ortho-substituted phenoxyacetic and phenylthioacetic acids were determined in dilute carbon tetrachloride solutions. The O–H stretching absorption of phenoxyacetic acids carrying o-methoxy-substituents shows three absorption maxima, all of these being attributed to the monomeric species, and they are assigned to the free O–H group, the O–H group hydrogen bonded with α-phenoxy oxygen atom and the O–H group hydrogen bonded with methoxyl oxygen atom in the order of decreasing frequency. The O–H stretching absorption at the lower frequency of o-methoxyphenylthioacetic acids is also assigned to the hydrogen bonded monomeric species in which the chelation occurs between the carboxylic O–H group and the methoxyl oxygen atom.
Electric Conduction and Density of Condensed Phosphoric Acids and Their Mixtures with Sulfuric Acid
Authors: Akiyama Akitane , Suzuki Tsuyoshi , Saji Takashi
Published: July 2006

The electrolytic conductivities and densities of condensed phosphoric acids have been measured in the P2O5 concentration range from 55% to 80% at 55.0, 70.0, and 90.0°C. Assuming the proton jump mechanism through the hydrogen bond network of H2O and H3PO4, the molar conductance was calculated and found to be constant in the P2O5 concentration range between 60% and 76%. The investigation has been extended to the mixtures of condensed phosphoric acids and concentrated sulfuric acid. The complex formation of [H4PO4+·HSO4−] and [H3O+·HSO4−] has been suggested in the mixture.
Synthesis of Nδ-Hydroxyornithine
Authors: Isowa Yoshikazu , Takashima Toshiyuki , Ohmori Muneki , Kurita Hideaki , Sato Masanari , Mori Kaoru
Published: July 2006

N δ-Tosyl-Nδ-benzyloxy-Dl-ornithine was synthesized starting from γ-(N-tosyl-N-benzyloxy)-aminopropyl bromide and diethyl acetamidomalonate and resolved enzymatically to give the l- and d-isomers. Removal of one or both of protecting groups gave Nδ-benzyloxyornithine or Nδ-hydroxyornithine. The reduction product of Nδ-hydroxy-l-ornithine was identical with authentic l-ornithine.
Preparation and Thermal Decomposition of 1,4,5- and 1,3,5-Trimethyltetrazolium Iodides
Authors: Isida Tyûzô , Kozima Sinpei , Fujimori Shin-ichirô , Sisido Keiiti
Published: July 2006

1,4,5- and 1,3,5-Trimethyltetrazolium iodides were prepared by the reaction of methyl iodide with 1,5- and 2,5-dimethyltetrazoles, and the reaction of methyl iodide with 5-methyltetrazole. The latter method is more facile for the preparation of these iodides. Upon thermal decomposition of the 1,3,5-trimethyl salt at 130°C, the 1-methyl group was eliminated predominantly to yield 2,5-dimethyltetrazole. When the 1,4,5-trimethyl salt was decomposed at 270°C, a mixture of 1,5- and 2,5-dimethyltetrazole was obtained in 74% and 21% yields, respectively. For the formation of 2,5-dimethyltetrazole from the 1,4,5-trimethyl salt, there has been shown an intermolecular methylation scheme that the 1,4,5-trimethyl salt methylated 1,5-dimethyltetrazole being formed in situ to give the 1,3,5-trimethyl salt.
Copper(I) Perchlorate Complexes of Allyl, 2-Methylallyl and cis-and trans-2-Butenyl Alcohols
Authors: Ishino Yoshio , Ogura Tetsuya , Noda Kenichiro , Hirashima Tsuneaki , Manabe Osamu
Published: July 2006

[Cu(allyl alcohol) (H2O)]ClO4 (abb. Cu(all)(H2O)ClO4), [Cu(allyl alcohol)2(H2O)]ClO4 (abb. Cu(all)2-(H2O)ClO4), [Cu(2-methylallylalcohol)(H2O)]ClO4 (abb. Cu(meth)(H2O)ClO4) and [Cu(cis- and trans-2-butenyl alcohol)2 (H2O)]ClO4 (abb. Cu(cis-and trans- but2 (H2O)ClO4) were synthesized. It was shown by means of equivalent conductance that Cu(all)(H2O)ClO4 is a strong electrolyte of uni-uni valent in acetone. The molecular weight of Cu(all)(H2O)ClO4 obtained from measurements of the direct vapor-pressure depression of acetone showed that the complex is monomeric. The C=C stretching band of the allylic alcohol shifts by about 100 cm−1 to the lower frequency side upon coordination. The chemical shifts of the vinyl protons in these complexes shift by about 0.5–1 ppm to the higher frequency side than those of free alcohols. It was concluded that the allylic alcohol coordinates to the copper atom through both the double bond and the oxygen atom. The equilibrium constant corresponding to Cu(trans-but)+2(H2O)ClO4+2cis-2-butenyl alcohol=Cu(cis-but)+2(H2O)ClO4+2trans-2-butenyl alcohol in 2-butenyl alcohol was estimated to be 9.82 at 25°C and the enthalpy change was estimated to be −3.13kcal/mol.
The Synthesis and Configuration of Fukiic Acid Derivatives
Authors: Matsumoto Takashi , Hidaka Kazuo , Nakayama Teruko , Fukui Kenji
Published: July 2006

The methylation of 3,4-dimethoxyphenylpyruvic acid (II) gave the corresponding methyl ester (III), which was then subjected to a Wittig reaction with carbomethoxymethylenetriphenylphosphorane to give the corresponding fumaric (IVa) and maleic (IVb) acid derivatives in a 1:3 ratio. The cis-hydroxylation of IVa and IVb with an aqueous solution of potassium permanganate and magnesium sulfate gave methyl (±)-thero-2,3-dihydroxy-4-(3,4-dimethoxyphenyl)-3-methoxycarbonylbutyrate (Va) and its (±)-erythro-isomer (Vb) respectively. The dimethyl esters, (±)-Va and (±)-Vb, were converted to the corresponding monomethyl esters, (±)-VIIa and (±)-VIIb respectively, via two dicarboxylic acid derivatives, (±)-VIa and (±)-VIb. The resolution of (±)-VIIb with brucine gave (+)-VIIb and (−)-VIIb, which were then converted to (+)-Vb and (+)-VIb and to (−)-Vb and (−)-VIb respectively. The synthetic (+)-Vb was shown to be identical with the natural O,O′-dimethylfukiic acid dimethyl ester by a mixed fusion and by comparisons of their IR and NMR spectra. From the present study it is evident that natural fukiic acid has an erythro configuration.
The Substituent Effect. IV. Proton NMR Chemical Shifts of Phenols
Authors: Tsuno Yuho , Fujio Mizue , Takai Yoshio , Yukawa Yasuhide
Published: July 2006

NMR chemical shifts of the hydroxyl proton of m- and p-substituted phenols were determined in aprotic DMF and DMSO solutions. The effect of substituents on the hydroxy chemical shift was correlated much more excellently with our LArSR relationship, Δδ=ρ(σ0+rΔ\barσ\barR), than with simple Hammett equation, ρσ0 or ρσ−. The correlation resulted in ρ=1.655 and r=0.639 in DMF with correlation coefficient 0.9992 and ρ=1.530 and r=0.673 in DMSO with a correlation coefficient 0.9990. Anisotropy effect of any substituent was not significant. The deviations of particular substituents were ascribed to the modification of the electronic characters of substituents due to strong substituent-solvent interactions in DMF (or DMSO). The inductive and resonance substituent constants, (σi)DMF and (Δ\barσ\barR)DMF, were determined, on the basis of the assumption that the solvent-modification of a given substituent is practically the same at both meta and para positions.
Preparation of Reinforcing Fillers from Japanese Acid Clays with Lime and by Calcination. I. Availability of Raw Materials for Preparing Hard Clay and the Properties of Products
Authors: Rai Hideki , Yamada Junkichi
Published: July 2006

Reinforcing fillers for elastomers were prepared from three representative specimens of Japanese acid clay by treatment with hydrated lime (CaO 10%), subsequent calcination (600°C, 1.5 hr), and mechanical disintegration. Physicochemical properties of the products such as hygroscopicity, pH, diphenylguanidine (DPG) adsorption, specific gravity, and bulk density were determined in comparison with those of raw materials. Morphological and structural features were investigated by means of electron microscopy, X-ray diffraction, infrared and far infrared spectroscopy, DTA, and TGA. The reinforcing effects on SBR-1502 were compared with those of Dixie Clay and Silene EF. The following results were obtained. (1) Acid clays containing montmorillonite and α-cristo-balite as principal constituents are suitable for the preparation of the fillers, but not the clay containing halloysite mineral as a major component in the randomly mixed-layers of kaolinite and montmorillonite with no excess silica. (2) Irreversible contraction as well as the formation of calcium silicates took place in montmorillonite minerals. Calcium silicate is formed in two states, one covering the surface of montmorillonite minerals and the other being set free. This gives rise to remarkable changes in adsorptivity, pH, swelling, bulk density, and specific gravity. Thus it becomes possible to use acid clays as reinforcing fillers. Hygroscopicity and the pH could be made about the same as those of Silene EF. The DPG adsorption capacities could be reduced as low as that of Dixie Clay. The products thus obtained greatly increased in bulk density and exhibited an average property of Dixie Clay and Silene EF in reinforcing SBR-1502.
The Determination of the Diffusion Coefficient and the Maximum Surface Concentration of Polyvinylpyrrolidone by Means of a Hanging Mercury Drop Electrode
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Nomoto Shigemitsu
Published: July 2006

Subsequently to the previous work with a dropping mercury electrode (DME), the diffusion coefficient (D) and the maximum surface concentration (Γm) for polyvinylpyrrolidone (PVP) were determined in a In sulfuric acid solution by means of a hanging mercury drop electrode (HMDE). The values of D and Γm for PVP were obtained separately by means of the equation for a semi-infinite spherical diffusion for HMDE. The results for D were compared with the values evaluated from the Stokes-Einstein equation or with those previously published. The results for Γm are also shown in comparison with those values to be expected from the data obtained by the use of DME or HMDE on the assumption of linear diffusion and D, or in comparison with the results published by Jehring. It was also confirmed that the HMDE used by the authors is almost satisfactory for the determination of D and Γm in this case.
Electronic Structures of Thianthrene, Phenothiazine, and Related Heterocyclic Compounds
Authors: Kamiya Mamoru
Published: July 2006

Systematic studies were made on thianthrene, phenoxathiin, diphenylene dioxide, phenothiazine, and phenoxazine for the correlation between the folded structure and electronic spectra in terms of the semiempirical SCF–MO–CI method. The calculated results are in good agreement with the experimental results, the folded structure being prominent in the sulfur-containing molecules. The dihedral angle dependency of the all valenceelectronic energy and ionization potential was also studied by the extended Hückel method.
The Solvent Extraction of Zinc(II) in Sodium Perchlorate-halide Solutions with Trioctylphosphine Oxide
Authors: Moriya Hiromitsu , Sekine Tatsuya
Published: July 2006

The solvent extraction of zinc(II) in 1m sodium perchlorate ionic media containing chloride, bromide, or iodide ions at 25°C was determined as a function of the halide-ion (X−) concentration by using the zinc-65 tracer. From the extraction data with isopropyltropolone (IPT) in chloroform, the formation of the ZnX+ complex was observed, but the stability constants of these complexes were not large (ZnCl+: β1 is 100.00, ZnBr+: β1 is less than 10−0.5and the formation of ZnI+ is negligible), and the higher complexes were negligible in all cases. The extraction of zinc(II) from these media with methylisobutylketone (MIBK) was not effective, although the extracted species could be identified as ZnX2. The extraction with trioctylphosphine oxide (TOPO) in hexane, on the other hand, was much better than that with MIBK. From the distribution ratio determined as a function of the halide and TOPO concentrations, the extracted species were concluded to be Zn(ClO4)2(TOPO)4, ZnX(ClO4)(TOPO)3, and ZnX2-(TOPO)2. The extraction constants for these species were determined by a graphic analysis of the data, and it was concluded that the extractabilities are larger in the order: iodide>bromide>chloride. From these data, it is clear that, if a suitable and effective neutral extractant is employed, the extractions of the above complexes are possible, even from aqueous solutions in which practically no complex is formed.
Elimination Reactions of Ethylene Halohydrins on Solid Catalysts
Authors: Mochida Isao , Anju Yasuhide , Kato Akio , Seiyama Tetsuro
Published: July 2006

Elimination reactions of ethylene chlorohydrin and ethylene bromohydrin were studied over solid acids, solid bases, and metals supported by silica gel at 300°C using a microcatalytic gas chromatographic technique in order to elucidate the relationship between the elimination selectivity and the nature of active sites. Acetaldehyde was exclusively formed on solid acids and MgO. However, ethylene oxide as well was formed on solid bases. The ratio seems to depend on the basic strength of the solid bases. On the metals, ethylene was formed in addition to acetaldehyde. The former was the principal product on Pd and Pt. From these results, it was concluded that acetaldehyde was formed on acidic sites by halide-ion abstraction; ethylene oxide, on basic sites by proton abstraction, and ethylene, on less polar sites of metals by halogen atom abstraction.
Liquid-phase Adsorption from Binary Solutions on Silica Gel. The Apparent Separation Factors and the Distribution of Adsorption Sites
Authors: Kagiya Tsutomu , Sumida Yūzō , Tachi Toshihiro
Published: July 2006

The liquid-phase adsorption equilibrium of a cyclohexane-benzene mixture on a silica-gel surface, containing various quantities of physically-adsorbed water, has been studied at 30°C. The apparent separation factors (αap) have been determined on the assumption that this liquid-phase adsorption is of the Langmuir-type. It was found that the values of αap were, in general, markedly affected not only by the composition of binary solvents, but also by the amounts of physically-adsorbed water. In order to discuss this point quantitatively, the theoretical equation for estimating the apparent separation factors on a complicated solid surface having two or more types of adsorption sites has been derived on the basis of the theory of chemical equilibrium. The following three types of adsorption sites have been assumed to exist on the silica-gel surface used in this experiment: the surface silanol (σ1), the monolayer of water (σ2), and the multilayer of water (σ3). The separation factors of the σ1 and σ3 were experimentally measured as 17.1 and 2.5. By best-fitting the above theoretical equation for αap with the observed values, the separation factor of the σ2 site was taken to be 3.7 and the distribution of each adsorption site on the surface was determined.
The Crystal and Molecular Structure of Dimethyltin Bis(N,N-dimethyldithiocarbamate)
Authors: Kimura Toshihide , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The crystal and molecular structure of dimethyltin bis(N,N-dimethyldithiocarbamate), [(CH3)2Sn{S2CN-(CH3)2}2], has been determined by single crystal X-ray diffraction. The crystals are orthorhombic; Fdd2; a=25.478±0.008, b=35.323±0.011, c=6.936±0.006 Å, Z=16. The tin atom has a distorted octahedral environment. The tin atom and the four sulfur atoms lie approximately on the same plane, with two Sn–S bond distances of 2.515±0.008 and 2.497±0.008 Å and two longer Sn-S distances of 2.954±0.007 and 3.061±0.008 Å, while the methyl groups are in trans positions; average Sn–C=2.15±0.04 Å. The SnSC(S)N skeletons on both sides of the tin atom are approximately planar, and the average bond distances are S–C=1.72±0.03, C–N=1.31±0.03, and N–C(Me)=1.49±0.04 Å.
An ESR Study of Some Substituted Pyridine N-Oxide Copper(II) Complexes
Authors: Freyberg Derek P , Isobe Toshiyuki , Misumi Seizo
Published: July 2006

The ESR (methanol solution, frozen solution, powder, and single crystal) spectra of [CuL4](ClO4)2, where L=pyridine N-oxide, α-picoline N-oxide, β-picoline N-oxide, γ-picoline N-oxide, and 2,6-lutidine N-oxide, and of [CuL6](ClO4)2, where L=pyridine N-oxide and γ-picoline N-oxide, have been obtained. The preparation of hexa(γ-picoline N-oxide) copper(II) perchlorate is reported. The solution and frozen solution spectra indicate a very similar bonding in all the complexes, with moderately ionic metal-oxygen. The powder spectra reveal all the tetrakis complexes to be axially symmetric; though tetra(γ-picoline N-oxide) copper(II) perchlorate shows a reversal of the usual order of the g-values. This is explained in terms of the packing interactions within the crystal structure, rather than metal-ligand interaction. All the single crystal spectra are characteristic of axially symmetric complexes. Hexa(pyridine N-oxide)copper(II) perchlorate gives an isotropic ESR spectrum, but this does not seem to be due to exchange interaction. Hexa(γ-picoline N-oxide)copper(II) perchlorate gives an axial ESR spectrum with a considerable tetragonal misalignment.
Transfer-hydrogenation and Transfer-hydrogenolysis. I. Transfer-hydrogenation of Cyclooctadienes Catalyzed by Dichlorobis(triphenylphosphine)iron(II)
Authors: Nishiguchi Takeshi , Fukuzumi Kazuo
Published: July 2006

Hydrogen transfer from a number of organic compounds to olefins in a homogeneous system was studied. In the case of hydrogen transfer to 1,5-cyclooctadiene, using dichlorobis(triphenylphosphine)iron(II) as the catalyst, dihydroxybenzenes, such as pyrocatechol and hydroquinone, were much superior to prim- and sec-alcohols, 1-dodecanethiol, and cyclohexene as hydrogen donors.
Far Infrared Spectra and the Calculation of Lattice Vibrations of Benzoic Acid
Authors: Meshitsuka Shunsuke , Takahashi Hiroaki , Higasi Keniti , Schrader Bernhard
Published: July 2006

Polarized far infrared spectra from 400 to 30 cm−1 of benzoic acid single crystals have been measured. Three bands polarized parallel to the C2s screw axis b were observed at 104, 86, and 62 cm−1, and three bands polarized parallel to the a-axis at 106, 76, and 65 cm−1. The lattice vibrations of benzoic acid have been calculated assuming the rigidity of the molecule during the lattice vibrations and applying a simple force field. The bands at 104, 86, and 62 cm−1 were assigned to the rotational vibrations of Au symmetry species: the O–H···O stretching, the ring torsional and the O–H···O out-of-plane bending modes, respectively, and the bands at 106, 76, and 65 cm−1to those of Bu symmetry species. The force constant K(O···H) related to the hydrogen bonds in the cyclic dimer was calculated to be 0.35 mdyn/Å.
The Abnormal Absorption Intensity of the C–H Stretching Vibration Band in Chloroform Vapor. II.
Authors: Miyazaki Tomoo , Yamamoto Hiroshi
Published: July 2006

By CNDO calculations considering the 3d orbitals of the chlorine atom, the infrared absorption intensity of the C–H stretching vibration band in chloroform vapor has been discussed in comparison with those of methyl chloride and methylene chloride. The absolute intensities of the fundamental and the first-overtone bands of these compounds have been calculated in view of the mechanical and the electrical anharmoniciteis of the vibrating bond. From the results of these calculations, it was revealed that the contribution of the electrical properties of the vibrating bond to the abnormal absorption intensity of the C–H stretching vibration band in chloroform vapor is really greater than that of the mechanical anharmonicity.
The Reactions of 80Br Activated by the (n,γ) Process with Methane
Authors: Saeki Masakatsu , Numakura Kenshi , Tachikawa Enzo
Published: July 2006

The reactions of 80Br activated by the (n,γ) process with CH4 have been examined. By assuming that the limiting yields of products at 1.0 m.f. of the Kr-moderator is due to thermal ionic processes, the kinetic yields were tentatively determined to be the 12.4% for total organic, 11.4% for CH380Br, and 1.0% for CH280BrBr. A similar treatment of the results from the reactions with CD4 gives 5.1% for total organic, 3.9% for CD380Br, and 1.2% for CD280BrBr. When the CH380Br yield was compared with that from the reactions of 80Br from the (I.T.) activation, a noticeable difference was noticed; it was roughly 3 times as large as in the latter system. Furthermore, the pressure effects on the CH380Br show that a fraction of CH380Br is highly excited and is able to decompose even at a pressure of 1920 mmHg. This suggests that the distribution of 80Br in the reaction energy range extends to a higher energy than in the case of 80Br activated by the (I.T.) process.
Crystal Growth of β-Hopeite on (0001) Plane of a Single Crystal of Zinc
Authors: Okuwaki Akitsugu , Ninagawa Jinichi , Okabe Taijiro , Omori Keiichi
Published: July 2006

The epitaxy and the orientation of β-hopeite grown on the (0001) plane of a single crystal of zinc were studied. The epitaxy was found to be (0001)-Zn//(010)-β-hopeite, and the orientation was [10.0]//[100] or [12.0]//[100]. The nature of the chemical bond between β-hopeite and zinc is considered to be similar to that of the wurtzite type rather than to that of the wüstite type in view of the structure of the boundary surfaces.
Interaction between Organoaluminum Compounds and Ditertiary Phosphines Studied by Proton Magnetic Resonance
Authors: Kagawa Teruhiko , Hashimoto Harukichi
Published: July 2006

The adduct formation of triethylaluminum or diethylaluminum chloride with ditertiary phosphines (Ph2-P(CH2)nPPh2  n=1,2,3,4, and 6) in benzene solution was investigated by PMR. The adducts have a composition of (AlEt3)2 (diphosphine) except in the case of Ph2PCH2PPh2, which makes two kinds of adducts (1:1 and 2:1). Electronegativity of the complexed aluminum is also calculated from Dailey-Shoolery equation.
Thermal Properties of Copper(II) Chelates of Some 1,5-Alkylpentane-2,4-diones
Authors: Yoshida Isao , Oono Yoshitsugu , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

Thermally stable and low melting copper(II) chelates of β-diketones have been synthesized as follows; bis-(heptane-2,4-dionato)copper(II), mp 172°C; bis(nonane-4,6-dionato)copper(II), mp 162°C; bis(5-ethylheptane-2,4-dionato)copper(II), mp 72°C; bis(3-ethylnonane-4,6-dionato)copper(II), mp 50°C; bis(3,7-diethylnonane-4,6-dionato)copper(II), mp 58°C. Their thermal characteristics including enthalpy and entropy of fusion, have been discussed in relation with the molecular structure of the copper chelates.
Studies on Stable Free Radicals. XI. ESR Spectra of Stable Nitroxide Biradicals
Authors: Toda Toshimasa , Mori Eiko , Murayama Keisuke
Published: July 2006

The ESR spectra of the triplet state of stable nitroxide biradicals, 1,9-diaza-2,2,8,8,10,10-hexamethyl-4-oxospiro[5.5]-undecane-1,9-dioxyl (III), cyclohexane-1-spiro-2′-(4′-oxoimidazolidine)-5′-spiro-4″-(2″,2″,6″,6″-tetramethylpiperidine)-1′, 1″-dioxyl (IV) and cyclohexane-1-spiro-2′-(3′-oxoimidazolidine)-5′-spiro-4″-(2″,2″,-6″,6″-tetramethylpiperidine)-1′,1″-dioxyl (V) have been observed in a frozen MTHF glass. The biradicals have 2D\simeq500 and E\simeq0 gauss. The distance (I\simeq5 Å) between the two radical sites in these biradicals indicates that one piperidine ring can exist in chair form and the other in twisted form in III, and both in the twisted form in IV and V. The biradical, 2,2,6,6-tetramethylpiperidine-4-spiro-2′-(4′-oxoimidazolidine)-5′-spiro-4″-(2″,2″,-6″,6″-tetramethylpiperidine)-1,1″-dioxyl (VI) in a MTHF frozen glass shows no spectrum corresponding to a triplet state.
Intramolecular Hydrogen Bonds. XVIII. Intramolecular Hydrogen Bonding in Ethyl α- and β-Alkylamino-alkanoates
Authors: Mori Nobuo , Aihara Masanori , Asabe Yoshihiro , Tsuzuki Yojiro
Published: July 2006

The intramolecular hydrogen bonding in ethyl ω-alkylamino-acetates and -propionates in dilute carbon tetrachloride solutions has been investigated through the measurement of the NH and CO stretching absorption spectra. In the α-esters, the spectral data give no evidence regarding the hydrogen-bond formation. In the β-esters, though, the hydrogen bonding occurs, probably predominantly between the NH and the CO group.
Studies on Separation of Amino Acids and Related Compounds. VII. Separation of l-Aspartyl-(α,β)-l-histidine and of l-Glutamyl-(α,γ)-l-histidine
Authors: Hirata Mitsuteru , Noda Kosaku , Izumiya Nobuo
Published: July 2006

As control compounds, the structural α- and ω-isomers of l-aspartyl- and l-glutamyl-l-histidine were synthesized by a conventional manner. The experiments on a column chromatography of Dowex 50 were carried out with a model mixture containing α- and ω-isomer, and the complete separation of the isomers was observed at acidic condition. A mixture of α- and ω-isomers of l-aspartyl- or l-glutamyl-l-histidine prepared through the coupling of benzyloxycarbonyl-l-aspartic or glutamic acid anhydride with l-histidine were separated into each isomer with a large column in moderate yields.
The Reduction of Stereoisomeric 6-tert-Butyl-3-methoxy-3-methylcyclohexenes with Lithium in Ethylamine
Authors: Masamune Tadashi , Matsue Hajime , Fujii Matsuo
Published: July 2006

The synthesis and reduction with lithium in ethylamine of the entitled stereoisomeric allyl ethers 1 and 2 are described. The reaction of both the isomers occurred very readily with concomitant cleavage of the methoxy groups, and gave the same products, 4-tert-butyl-1 -methylcyclohexene (13), and c- and t-3-tert-butyl-6-methylcyclohex-1-enes (14 and 15), in the same ratio (87 : 4 : 9), indicating that the respective reactions involved a common intermediate (16). Moreover, the reduction of the cis-isomer 1 with an axial methoxy group proceeded much more rapidly than that of the trans-isomer 2 with an equatorial methoxy.
Methylene Analogs of Cyclobutenedione. III. The Reaction of 2-Bromo- and 2,2-Dibromo-3,4-bis(diphenylmethylene)cyclobutanone with Alcoholic Potassium Hydroxide
Authors: Toda Fumio , Takehira Yoshikazu
Published: July 2006

The reactions of 2-bromo-3,4-bis(diphenylmethylene)cyclobutanone (III) with methanolic and 2-propanolic potassium hydroxide afforded methyl 4-methoxy-2,3-bis(diphenylmethylene)butyrate (VIII) and 3,4-bis-(diphenylmethylene)-γ-lactone (XXI) respectively. The reaction of the 2,2-dibromo analog of III (XXV) with methanolic potassium hydroxide afforded methyl 4-methoxy-4-bromo-2,3-bis(diphenylmethylene)butyrate (XXVIIIa) and methyl 4,4-diphenyl-3-formyl-2-diphenylmethylenebut-3-enate (XXIIIa) in approximately equal yields. However, the reaction of XXV with 2-propanolic potassium hydroxide afforded XXIIIc exclusively. The reaction mechanism was disclosed to be that the haloester intermediates V and XXVII initially formed from III and XXV respectively, by the addition of alcohol to the carbonyl followed by the ring-opening, react with the alkoxy and hydroxy anions competitively.
Isolation and Structure Proof of Dinitrocyclohexenones Formed in the Nitration of Polyalkylbenzenes with Fuming Nitric Acid
Authors: Suzuki Hitomi , Sawaki Mikio , Sakimoto Reiji
Published: July 2006

Action of fuming nitric acid upon 1,2,3,5-tetramethylbenzene and 2-ethyl-1,3,5-trimethylbenzene at low temperature was found to yield small amounts of dinitrocyclohexenones in addition to the ring nitration and side-chain nitrooxylation products. Chromatographic separation over silica gel followed by spectral investigation established the structures of these nitro-ketones to be 2,3,4,6-tetramethyl-5,6-dinitro-3-cyclohexen-1-one and 2,4,6-trimethyl-3-ethyl-5,6-dinitro-3-cyclohexen-1-one respectively. The mechanistic interpretation of their formation was briefly discussed.
The Photo-Beckmann Rearrangement of 3α,5-Cyclo-5α-cholestan-6-one Oxime
Authors: Suginome Hiroshi , Takahashi Hajime , Masamune Tadashi
Published: July 2006

Photolysis of 3α,5-cyclo-5α-cholestan-6-one oxime affords two isomeric lactams with cyclopropane rings arising from photo-Beckmann rearrangement although the yields are poor. The result gives further support to our view on the C→N migration process in photo-Beckmann rearrangement. The major part of the products of the reaction consisted of the parent ketone and several products probably derived from it. The results are compared with those obtained in our photolysis of 5α-cholestan-6-one oxime and the isomeric 5β-cholestan-6-one oximes. The poor yields of the lactams is probably ascribable to the presence of the cyclopropane ring in this conjugated cyclopropyl ketone oxime.
The Structure of κ-Carrageenan from Gigartina Tenella
Authors: Hirase Susumu , Watanabe Kyoko
Published: July 2006

An alkaline treatment of κ-carrageenan from Gigartina tenella resulted in the change of the proportions of galactose, 3,6-anhydro-galactose and sulfate from 100 : 91 : 124 to 95 : 96 : 119. Fragmentation of the methylated polysaccharide gave 2,4,6-tri-O-, 2,6-di-O-, and mono-O-methyl-d-galactose in the molar proportions of 1 : 18 : 0.8 together with 3,6-anhydro-d-galactose and its 2-O-methyl-derivative in the molar proportion of 1 : 4. From these and other data, it is concluded that the polysaccharide is composed of the residues of 1,3-linked β-d-galactose 4-sulfate (95 mol), 1,4-linked α-d-galactose 6-sulfate (5 mol), and 1,4-linked 3,6-anhydro-α-d-galactose (67 mol) and its 2-sulfate (24 mol), and that the 1,3- and 1,4-linked residues are repeated alternatingly to form a chain macro-molecule.
Studies on Stable Free Radicals. XII. ESR Spectra of 2-t-Butylaminotropone N-Oxyl Radicals
Authors: Toda Toshimasa , Mori Eiko , Murayama Keisuke
Published: July 2006

We observed a well resolved ESR spectrum of 2-t-butylaminotropone N-oxyl radical generated by the oxidation of the corresponding amine with perbenzoic acid, and assigned the values of hyperfine coupling constants of protons in the tropone ring by a comparison with the ESR spectra of deuterium substituted 2-t-butylaminotropone N-oxyl radicals: aN=12.7 gauss, aH3=aH5=aH7=1.86 gauss and aH4=aH6=0.93 gauss for protons on tropone ring.
The Oxidation of (+)-3-Carene and the Related Compounds with t-Butyl Chromate
Authors: Suga Takayuki , Shishibori Tsuyoshi , Matsuura Tamon
Published: July 2006

The oxidation of (+)-3-carene with t-butyl chromate was found to afford 3,α-dimethylstyrene (2), eucarvone (3), 1,1,4-trimethylcyclohepta-2,4-dien-6-one (4), 3-methylacetophenone (5), 8-hydroxy-m-cymene (6), car-3-en-2-one (7), (−)-car-3-en-5-one (8), and (−)-car-3-ene-2,5-dione (9). The aromatized compound (6) was a major product in the oxidation in an acidic medium, whereas the oxidation in the neutral and the basic media gave the enedione (9) and the enone (8) as major products. It was, furthermore, proved that methylenes adjacent to the cyclopropane ring of (−)-cis-carane (10) and (+)-caran-3β-ol (11) were scarcely attacked by t-butyl chromate.
The 1-Methylene Derivatives of [7](2,6)Pyridinophane. Preparative and Conformational Studies
Authors: Fujita Shinsaku , Imamura Kazuo , Nozaki Hitosi
Published: July 2006

The 1-exo-methylene derivatives (IV, V and VII) of [7](2,6)pyridinophane (I) are synthesized by Wittig’s reaction of [7](2,6)pyridinophan-1-one (III) or by the dehydration of the corresponding carbinol (VI). The C-4 protons are all shielded magnetically to varying extents, depending on their respective 1-substituents. The shielding effect is ascribed to the anisotropy of the pyridine ring. The signals of the C-4 protons are temperature-dependent, and the energy barriers for the conformational changes are estimated to be 8.7 for III, 9.1 for IV, 9.1 for V and 9.8 kcal/mol for VII.
Synthetic Reactions by Complex Catalysts. XXVI. The Copper-catalyzed Reaction of α,β-Unsaturated Isocyanide with Active Methylene Compounds
Authors: Saegusa Takeo , Murase Ichiki , Ito Yoshihiko
Published: July 2006

The Cu2O-catalyzed reaction of α,β-unsaturated isonitrile with active methylene compound is described. Vinyl isocyanide (VIC) and propenyl isocyanide (PPIC) were employed as the isocyanide components. In addition, allyl isocyanide (AIC), which has been known to be rearranged readily to PPIC by Cu2O, was also used as a precursor of PPIC. Five types of products were isolated and identified. These products were explained by a scheme starting with an intermediate of the organocopper-isonitrile complex (9) derived from the active methylene compound.
The Synthesis of the 1,2,4-Thiadiazine-1,1-dioxides
Authors: Hasegawa Kiyoshi , Hirooka Syuzi
Published: July 2006

N-(2-Phenylethene-1-sulfonyl)-N′-monoalkyl S-methylisothioureas, 2, were ring-closed to yield Michael cycloadducts, 3-methylthio-4-alkyl-5-phenyl-1,1-dioxo-5,6-dihydro-1,2,4-thiadiazines, 3. Bulky N′-alkyl groups hindered the cycloaddition. The base-catalyzed hydrolysis of 3 and 3-chloro-derivatives 4 gave 4-methyl-5-phenyl-2,3,5,6-tetrahydro-1,1,3-trioxo-1,2,4-thiadiazines, 5, which in turn underwent N-alkylation to give 6. The reaction of 4 with amines or with sodium methoxide yielded 3-amino-, 7, or 3-methoxy-thiadiazine derivatives, 9.
The Effect of the Wavelength of an Exciting Light on Four-center-type Photopolymerization in the Crystalline State
Authors: Tamaki Takashi , Suzuki Yasuzo , Hasegawa Masaki
Published: July 2006

The effect of the wavelength of an exciting light on four-center-type photopolymerization in the crystalline state has been investigated. 2,5-Distyrylpyrazine (DSP), 1,4-bis[β-pyridyl-(2)vinyl]benzene (P2VB), p-phenylenediacrylic acid (p-PDA) dimethyl ester were converted quantitatively into highly crystalline oligomers (pentamers on the average) on irradiation at the long-wavelength edge of the absorption of the monomer. On subsequent exposure to the light which is absorbed by each oligomer, the oligomer crystals as-polymerized were converted quantitatively into high polymer crystals. The polymer thus obtained was found to be identical with the polymer produced by the light of a xenon or a high-pressure mercury lamp. The quantum yields for the oligomerization and polymerization reactions of DSP and the p-PDA dimethyl ester were found to be between 1 and 2 on the basis of the number of olefinic double bonds consumed to form the cyclobutane ring. These results confirmed that the four-center-type photopolymerization in the crystalline state consists of two kinds of separable, step-by-step addition mechanisms: an oligomerization of the dioleflnic compound and a growth reaction of the terminal group in the growing chain. From the crystallographic information on the DSP oligomer, the oligomerization as well as the polymerization process of DSP were concluded to proceed by a monomer lattice-controlled mechanism.
Conformations of the Esters. VI. The Conformations of Monothiocarbonates
Authors: Oki Michinori , Nakanishi Hiroshi
Published: July 2006

The presence of two or three conformational isomers in monothiocarbonates has been confirmed by nuclear magnetic resonance and infrared spectroscopies and by dipole moment techniques. The data can best be interpreted by assuming that the conformations involving the s-cis conformation are more stable than that of s-trans, s-trans.
Oxidation by Transition Metal Complexes. V. Oxidation of Vinyl Esters Catalyzed by Rhodium Complex.
Authors: Takao Kiyotomi , Azuma Hiromichi , Fujiwara Yuzo , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

The oxidation of styryl acetate, vinyl acetate, vinyl propionate, methyl acrylate, and methyl cinnamate with RhCl(PPh3)3 catalyst has been studied. The reaction is remarkably affected by the substituent on an olefinic carbon atom. The oxidation mechanism was discussed in connection with decarbonylation.
The Additive Effect of Triphenylphosphine on the Polymerization of Vinyl Monomers by Copper(II) Chelates
Authors: Shono Toshiyuki , Yamashoji Yuko , Shinra Koichiro
Published: July 2006

Various copper(II) chelates were found to be effective initiators in the polymerization reaction of the methyl methacrylate in the presence of triphenylphosphine. The conversion increases with an increase in the concentration of triphenylphosphine, reaching a constant level at the ratio of 1: 2 between copper chelates and triphenylphosphine. Di-μ-methoxo-bis(ethylacetoacetato)dicopper(II) was the most effective initiator. The dependence of the rate of the polymerization on the square root of the concentration of the complexes suggests that the polymerization by this initiation system proceeds via a radical mechanism. It can be assumed that the copper chelate coordinated the triphenylphosphine and that homolytic fission occurred to give a free ligand radical, accompanied by the reduction of the central copper atom. Stable copper (I) mixed chelates were obtained under conditions similar to those of the polymerization.
The Reaction Mechanism of 2-Dimethoxymethyl-3-methoxypropionitrile with Acetamidine. II. A Novel Reaction Pathway
Authors: Nishino Takenori , Kiyokawa Masumi , Miichi Yoshiyuki , Tokuyama Kanji
Published: July 2006

The reaction of 2-dimethoxymethyl-3-methoxypropionitrile (1) with acetamidine produces pyrimidopyrimidine (8) via the consecutive process of 1→an intermediate→8. The intermediate was not isolated, but two structures have been proposed for it. We have now succeeded in the isolation of the intermediate and determined it to be 2-methyl-4-amino-5-dimethoxymethyl-5,6-dihydropyrimidine (4). Several key intermediates were also successfully isolated. The novel reaction pathway for the title reaction was concluded to be as follows: the elimination of methanol from 1, followed by the addition of acetamidine affords 3-acetamidinopropionitrile (3), the subsequent quick cyclization of which produces the intermediate, 4; the further elimination of methanol from 4, followed by a replacement reaction with acetamidine, gives an acetamidinomethylene compound (6), which is converted into the final product, 8, via an intermediate (7). Some minor pathways will also be presented.
The Reaction of Aspartyl Dipeptide Esters with Ketones
Authors: Ariyoshi Yasuo , Sato Naotake
Published: July 2006

The methyl and ethyl esters of α-l-aspartyl-l-phenylalanine (I and II), -l-tyrosine (III and IV), -l-(β-cyclohexyl)alanine (V and VI), and -l-[β-(4-hydroxycyclohexyl)]alanine (VII and VIII) have been found to react with ketones (acetone, methyl ethyl ketone, and cyclohexanone), in the absence of any catalysts, to give the corresponding 4-imidazolidinone derivatives (XVII–XXX). The NMR spectra of the imidazolidinones with an aromatic side chain (XVII–XXVIII) have indicated that these compounds exist in the folded conformation (in which the aromatic ring faces the imidazolidinone ring) in the solution. The imidazolidinones (XVII–XXX) were hydrolyzed with hot water to give the peptide esters (I–VIII), all in their original optical purity. On the other hand, the β-isomers of the peptide esters (IX–XVI) did not react with these ketones under the same conditions. These characteristics were used successfully in the separation of the two structural isomers of these peptide esters.
The Reaction of Sulfilimine with Phenyl Grignard Reagent
Authors: Oae Shigeru , Yoshimura Toshiaki , Furukawa Naomichi
Published: July 2006

The reactions of diphenyl (I), phenyl benzyl (II), and phenyl methyl N-p-tosylsulfilimines (III) with phenylmagnesium bromide were carried out. (I) gave biphenyl and diphenyl sulfide in high yields. A tracer experiment with diphenyl sulfilimine-1-14C revealed that the reaction proceeds via the initial formation of triphenylsulfonium salt upon which the attack of phenylmagnesium bromide affords the products. “Benzyne” mechanism is ruled out. (II) and (III) gave various compounds, the major products being α-phenylated sulfides which are presumed to be formed by the Pummerer type rearrangement initiated by the abstraction of α-proton by the Grignard reagent.