bluuebunny/crossref_metadata_2025 huggingface dataset:
The Reaction of Carboxylic Acids and Hydrocarbons in a Silent Electric Discharge. II. The Reactions of Ethylene with Methyl Acetate and with Acetic Anhydride
Authors: Hiraki Teruo
Published: July 2006

The present study was undertaken in order to ascertain the difference, if any, in the chemical behavior of methyl acetate and acetic anhydride submitted to a silent discharge between that in the presence and that in the absence of ethylene. (1) In the reaction of methyl acetate without ethylene, the main products were methanol, diacetyl, liquid hydrocarbons, formaldehyde, methane, carbon dioxide, carbon monoxide, and hydrogen. Although the methanol yield was almost the same, regardless of the presence or absence of ethylene, the yields of the hydrocarbons, all the carbonyl compounds, and of n-butyl acetate increased in the presence of ethylene. The great quantity of methanol produced might indicate that C–OCH3-bond breaking in the methyl acetate occurs preferably upon the discharge. (2) With acetic anhydride, on the other hand, acetaldehyde, acetone, ethyl acetate, ethyl methyl ketone, diacetyl, hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen were obtained as the main products. The yields of acetone and diacetyl decreased remarkably in the presence of ethylene, while the yields of hydrocarbons, ethyl methyl ketone, n-butyl methyl ketone, and of n-butyl acetate increased. The CH3COO· and CH3CO· radicals are thought to be the main intermediates in this reaction. The formation of n-butyl acetate and of n-butyl methyl ketone in the presence of ethylene can be explained on the basis of the telomerization of ethylene initiated by these radicals.
Intermolecular Hydrogen Bond Involving a π Base as the Proton Acceptor. VI. Hydrogen Bonding of Phenols and Naphthols to Aromatic Hydrocarbons. Entropy Anomaly and the Role of Charge-Transfer
Authors: Yoshida Zen-ichi , Ishibe Nobuyuki
Published: July 2006

Using a series of alkylphenols and naphthols as the proton donors, the hydrogen bond shifts and the association constants of hydrogen-bonded complexes involving methyl benzenes, naphthalene, and phenanthrene as the proton acceptors have been determined from the infrared spectra in carbon tetrachloride. The frequency shifts (Δv) of the hydroxyl stretching vibration and the free energy changes (−ΔF) for complex formation increase with decreasing pKa of the proton donors. Linear correlation between −ΔF and Δv are obtained for each proton donor interacting with methyl benzenes. The entropy anomaly discovered previously was confirmed. Chargetransfer arguments of Basila and co-workers are reconsidered for the hydrogen-bonded systems involving a π base as the proton acceptor.
Intermolecular Hydrogen Bond Involving a π Base as the Proton Acceptor. VII. Substituents and Steric Effects in the Hydrogen Bonding of 2,6-Xylenols to Mesitylene
Authors: Yoshida Zen-ichi , Ishibe Nobuyuki
Published: July 2006

Hydrogen bonding of 4-substituted-2,6-xylenols to mesitylene has been investigated by measurement of the hydroxyl stretching vibration. A linear relationship between the electronic effects of para substituents (Hammett σp constant) and the frequency shifts of the hydroxyl stretching vibration was obtained. A similar correlation was also observed with the free energy change associated with the formation of the hydrogen-bonded complex. The thermodynamic sutdies on the hydrogen bonding of 2,6-xylenol and phenol with both mesitylene and acetonitrile demonstrated the steric effect of 2- and 6-methyl groups on hydrogen bond formation. The free energy change for hydrogen bond formation with 2,6-xylenols as the proton donor was lower than with phenol. This is explained in terms of both entropy and enthalpy factors.
Nitroalkenylferrocene. IV. Preparation of 1-Ferrocenyl-2-iodo-2-nitroethylene and Configurations of Several Nitroalkenylferrocenes
Authors: Kono Hiromichi , Shiga Mikio , Motoyama Izumi , Hata Kazuo
Published: July 2006

A new method of synthesizing 1-ferrocenyl-2-iodo-2-nitroethylene (6) was presented, whereas 1-ferrocenyl-2-halo-2-nitroethylene could not be prepared by the usual method, involving the direct halogenation of the nitroolefin. The iodonitroethylene (6) was prepared by the reaction of the sodium salt of 1-ferrocenyl-2-nitroethylene with iodine or with potassium iodide. This procedure proved to be useful for introducing various groups on the α-carbon of the nitroethylene. The stereochemistry of nitroalkenylferrocenes, including some previously reported ones, was discussed on the basis of their spectral data.
Phenolytic Rearrangement and Isomerization of cis- and trans-4-t-Butylcyclohexyl p-Toluenesulfonates in a Phenol-Benzene Solvent
Authors: Okamoto Kunio , Saitô Seiki , Shingu Haruo
Published: July 2006

As the first examples of solvolytic cis-trans isomerization and 1,2-rearrangement for the 4-t-butylcyclohexyl system, phenolytic cis-trans (or trans-cis) isomerization and 1,2-rearrangement have been found for cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates in the phenol-benzene (1 : 1 by wt) solvent at 75.0°C. The tosylate, recovered after a 75% completion of the SN1 phenolysis of the cis-4-tosylate, was composed of small amounts of the trans-4-tosylate (1%) and the cis-3-tosylate (11%), besides 88% of the starting cis-4-tosylate, clearly indicating occurrence of both the cis-trans isomerization and the 1,2-rearrangement of the starting cis-4-tosylate. In a similar fashion, starting from the trans-4-tosylate, small amounts of the cis-4-tosylate (0.7%) and the trans-3-tosylate (2.6%) were recovered from the tosylate after the SN1 phenolysis was 75% complete. On the basis of the results of an examination into the influence of the added tosylate anion on the extent of isomerization and of rearrangement, it has been suggested that the cis-trans or trans-cis isomerization results largely from the external SN2-like attack of the tosylate anion on the SN1 ion-pair intermediate and partly as a consequence of the rotation of the t-butylcyclohexyl cation within the ion-pair intermediate, whereas the 1,2-rearrangement proceeds through an intramolecular 1,2-shift of hydrogen within the 4-t-butylcyclohexyl cation.
Kinetics of Isotopic Exchange between Acetylacetone-14C and Bisacetylacetonatopalladium(II) in Organic Solvents
Authors: Saito Kazuo , Takahashi Michihiko
Published: July 2006

Bisacetylacetonatopalladium(II) [Pd acac2] was precipitated crystalline free from excessive acetylacetone (Hacac) by adding the reaction mixture in anisole, benzene or 1,2-dichloroethane to chilled petroleum ether. Its specific counting rate was measured by liquid scintillation technique. The isotopic exchange rate is measurable at 40 to 80°C and the kinetics is expressed by the ordinary two term formula, Rate=[Pd acac2](k1+k2[Hacac]). The second term corresponds to the reagent path, in which acetylacetone molecule rather than acetylacetonate anion acts as nucleophilic reagent. The first term seems to express a dissociation mechanism rather than the solvent path; the break of Pd–O bond without the aid of nucleophilic attack by the solvent molecule is responsible for determining the exchange rate. The exchange reaction is accelerated by acids, and the acid-catalyzed reaction path operates independent of the reagent path to give the following kinetic formula:

Rate=[complex](k1+k2[Hacac]+k3[acid])
The Oxygenation-deoxygenation of Cobalt(II) Complexes on Polymers
Authors: Misono Akira , Koda Seiichiro , Uchida Yasuzo
Published: July 2006

Three cobalt(II) complexes, bis-(salicylaldehyde)-ethylenediimine-cobalt(II), bis-(salicylaldimino) cobalt(II), and di-(salicylal)-3,3′-diimino-di-n-propylamine-cobalt(II), were mixed with poly-4-vinylpyridine. These mixtures showed ESR signals which reversively appeared under oxygen. We tried to identify these signals on the basis of the electonic structure, cobalt(III)-O2−1. The oxygenation-deoxygenation rates were also observed and found to obey the Elovich rate equation.
Heat of Mixing for Binary Mixtures: Pyridine Derivatives + Benzene, and +Cyclohexane Systems
Authors: Murakami Takeshi , Murakami Sachio , Fujishiro Ryoichi
Published: July 2006

The heat of mixing was measured for binary mixtures of pyridine derivatives (α-picoline, β-picoline, γ-picoline, and 2,6-lutidine) with benzene or cyclohexane at 25.0±0.01°C, and for a binary mixture of pyridine with benzene, or cyclohexane, at 30.0±0.01°C. The small values of the heat of mixing for pyridine derivatives-a benzene system were interpreted as an indication of strong specific interactions between pyridine derivatives and benzene. By treating the results in the manner described in a previous paper (Bull. Chem. Soc. Japan, 39, 720 (1966)), the specific interaction energies of pyridine derivatives with benzene were estimated. The strengths of the molecular interaction energy were in the order: γ-picoline>pyridine>β-picoline>α-picoline>2,6-lutidine; the order was discussed in terms of the molecular complexes.
The N→O Acetyl Migration of 5-Substituted-2-pyrrolidinemethanols
Authors: Sakurai Hisayuki , Ishimaru Toshiyasu
Published: July 2006

In order to obtain information about the stereochemistry of a fused-ring system, cis and trans isomers of 5-methyl- and 5-phenyl-2-pyrrolidinemethanols were synthesized and rate constants for their N→O acetyl migrations were measured. Each product was a mixture of cis and trans isomers. For both 5-methyl and 5-phenyl derivatives, it was observed that trans isomers migrated faster than cis isomers. The results were discussed in relation to stereochemistry.
Magnetic Moments and d–d Bands of Copper(II) Halide Complexes with Substituted Pyridine N-Oxides and Some Related Ligands
Authors: Muto Yoneichiro , Kato Michinobu , Jonassen Hans B , Cusachs Louis Chopin
Published: July 2006

In order to test the substituent effect or the effect of variations in chemical structures on the demagnetization and d–d band shift in dimeric copper(II) halide complexes with pyridine N-oxides and some related ligands, a variety of electron-donating or electron-withdrawing substituents attached in 2-, 3- and 4-positions in the pyridine ring of the ligand were extensively studied. In these dimeric complexes, no correlation was observed between the Hammett’s σ constants and the observed d–d band positions or magnetic moments. However, irrespective of the nature of the substituents, a linear relation was observed to exist between the d–d band positions and the magnetic moments, indicative of a magnetochemical support for the interpretation of the spectrochemical series through the idea of symmetry-restricted covalency. For the monomeric complexes with the same ligands, a linear relation exists between Hammett’s constants and the d–d band positions for each series of the electron-donating and electron-withdrawing substituents. Experimental results indicate that the most important factor determining the non-applicability of Hammett’s Rule in these dimeric complexes is the steric condition of the metal ions which shields them from the influence of other molecules or ions. The larger demagnetization effect of the bromide ion compared to the chloride ion has been interpreted as due to its larger nephelauxetic effect. On the basis of the established structure of the parent compound, two pathways for superexchange interaction have been proposed. The importance of a σ type orbital overlap compared to the π type is discussed.
The Spectrophotometric Determination of Thorium(IV) with Bromopyrogallol Red
Authors: Tonosaki Kôichi , Sakai Takayoshi
Published: July 2006

Bromopyrogallol red reacts with thorium(IV) to form a stable complex with an absorption maximum at 645 mμ against a reagent blank. The maximum absorbance is obtained in the pH range of 5.6 to 5.9 when the solution is heated in a boiling water bath for 20 min. The color system obeys Beer’s law in the range 6 to 106 μg of thorium in 25 ml. The molar absorptivity of the complex is calculated to be 5.0×104 at 645 mμ. The sensitivity of the reaction is 0.004 μg thorium per cm2. The complex has the composition 1 to 2 in metal to ligand. The effect of diverse ions on the determination is also examined.
Effects of the Addition of Chlorohydrocarbons on the Oxidation of Propylene; A Consideration of the Negative Temperature Coefficient
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi
Published: July 2006

A small amount of allyl chloride, 1,1-dichloroethane, or chloroform was added to the reactant in the oxidation of propylene in an inert fluidized-bed reactor. A negative temperature coefficient is observed in the conversion of propylene and in the formation of various products, but not propylene oxide, in the experiments with allyl chloride or 1,1-dichloroethane added. The results of the chloroform-adding experiments show a positive temperature coefficient in the conversion of propylene and in the formation of gaseous products. The results of the work described here are discussed on the basis of the probable reaction scheme. The results of the chloroform-adding experiments support the proposed catalytic effect of the chlorocarbene on the decomposition of acetaldehyde. It is concluded that the negative temperature coefficient is attributable to the apparent inactivity of acetaldehyde (the branching agent) in the high-temperature region in this reaction atmosphere.
Molecular Orbital Treatment of Nitric Oxide Radicals. I. Electronic Structure and Spectrum of the H2NO Radical
Authors: Kikuchi Osamu
Published: July 2006

A theoretical treatment of the H2NO radical is presented. In the calculation, the approximate SCF method of Longuet-Higgins and Pople for open-shell molecules is applied to the valence electron system, the CNDO/2 approximation is adopted, and the molecular excited states are approximated by linear combinations of some doublet Slater determinants constructed by means of the SCF MO for the ground state. The results thus obtained for the electronic structure of the H2NO radical are discussed. The calculated spectrum for the H2NO radical shows that the longest wavelength band has the n→π* character, and the π→π* transition energy is smaller than that for the n→σ* transition. The π→π* transition energy, 5.77 eV, calculated by the method in which only the π-electrons were explicitly considered, indicated that the π→π* band falls into the area near 240 mμ. From the calculated results for the H2NO radical and the solvent effect on the absorption bands of aliphatic nitric oxide radicals, two bands, at 450 mμ, and 240 mμ, characteristic of the latter radicals have been assigned to the n→π* and π→π* transitions respectively.
Intramolecular Hydrogen Bonds. XIV. Correlation of the Hydroxyl and the Carbonyl Frequencies of Methyl Salicylates with Hammett’s Substituent Constants
Authors: Mori Nobuo , Asano Yuzuru , Tsuzuki Yojiro
Published: July 2006

The infrared OH and C=O stretching spectra of methyl 4- or 5-substituted salicylates have been measured in dilute carbon tetrachloride solutions, and the respective peak-frequencies have been correlated with ordinary Hammett’s σ-constants. The best linear relationship has been established between the γOH and the (σOH−0.38σCOOMe) values and between the γC=O and the (σCOOMe−0.49σOH) values, where σOH and σCOOMe are the σ-constants of a substituent with respect to the OH and the COOMe group respectively. Besides, in other internally-bonded phenol systems, including o-bromophenols, o,o′-dihalophenols, and salicylic acids, the plotting of the OH frequencies against the (σOH−AσX) values gave the best linear relationship, where A is a constant depending on the kind of proton acceptor, X. The value of A can be a measure of the electronic effects of the substituent, influencing the bonded OH frequency through X.
Synthesis of 1- and 2-Piperidinophenazine Derivatives
Authors: Endo Hideo , Tada Masao , Katagiri Ken
Published: July 2006

A number of new piperidinophenazines have been prepared by the reactions of various halogenophenazines and their oxides, including several new compounds, with piperidine. The halogenactivating effect of the oxide groups in 1- or 2-halogenophenazine oxides, which had previously been known, was also observed in the present piperidination. It has been found that 1-chlorophenazine was considerably less reactive than 2-chlorophenazine in the piperidination, that but the 5-oxide group in 1-chlorophenazine-5-oxide enhanced the reactivity of chlorine.
The Cooxidation of Hydrocarbons in the Liquid Phase. V. Determination of the Reactivity Ratios
Authors: Niki Etsuo , Kamiya Yoshio , Ohta Nobuto
Published: July 2006

The cooxidations of cumene (C) and tetralin (T) and of styrene (S) and tetralin were studied in the presence of azobisisobutyronitrile; the reactivity ratios, r, were obtained as rC=0.21 and rT=5.0 for the cumene-tetralin system at 80°C and as rS=2.7 and rT=0.49 for the styrene-tetralin system at 70°C. A new method for the determination of r values from the rates of cooxidation has been developed. The merits and demerits of several methods for the determination of r values are discussed. In cases where a large curvature, preferably a rate minimum, is obtained by plotting the rates against the reactant compositions, the determination from the rates of cooxidation may be most suitable. In other cases, the use of the copolymerization equation may be preferable by product analyses. The hydroperoxide method may be valid for some systems.
The Flow Properties of γ-Polyglutamic Acid Solutions in Capillary
Authors: Mineshita Takeshi , Matsumura Shigeru , Ono Hiromi , Watanabe Takehiko , Ono Sôzaburo
Published: July 2006

Dependence of the viscosity of the solution of γ-polyglutamic acid in eater at various pH’s on the bore-size of the capillary viscometer has been studied at 25°C at various concentrations (0.01–0.05 g/100 ml). Measurements were carried out with a Maron-Belner type low shear capillary viscometer with various capillary radii (1.9×10−2–7.6×10−2cm) within the shear stress range 0.2–20 dyn/cm2 at the capillary wall. The polymer solutions showed a non-Newtonian flow behavior and a capillary bore-size dependence and both of these properties were diminished with the decreasing of pH. This capillary bore-size dependence may be attributed to the geometric hindrance of the capillary wall to the thermal motion of the polymer molecules near the wall. The dissolved state of the polymer molecules in solutions of various pH’s has been studied by means of optical rotatory dispersions, flow birefringence and intrinsic viscosity. The dissolved state of the polymer solution as well as the capillary bore-size dependence were sensitive to pH. The polymer molecule in neutral and alkaline media may be in the form of a highly expanded chain and in acid medium in a contracted form having a some ordered chain conformation.
Zeeman Effect of Phosphorescence. II. Intensity Considerations on Pyrazine Phosphorescence
Authors: Azumi Tohru , Ito Mitsuo , Nagakura Saburo
Published: July 2006

The Zeeman splitting of pyrazine phosphorescence is observed. The amount of splitting is 1.4 cm−1 under the magnetic field of 15 kilogauss. This magnitude is just what one expects for the free spin, which means that the zero-field splitting parameters are small compared with the observed splitting. On the assumption of random orientations of the pyrazine molecules in the sample, the phosphorescence intensities from the three split subcomponents are expected to be in the ratio of 13g1 : 16g0 : 13g−1 where g’s represent populations. This expectation is roughly manifested in the experimental observation. Finally, the theoretical calculation of the zero-field splitting parameters, D and E, is attempted, and the results are interpreted in terms of the experimental data.
Studies of Purine N-Oxides. III. The Synthesis of Purine 3-N-Oxides
Authors: Kawashima Hideaki , Kumashiro Izumi
Published: July 2006

6-Methoxy- and 6-ethoxypurine 3-N-oxides were obtained by the direct oxidation of the corresponding 6-alkoxypurines with hydrogen peroxide in aqueous acetic acid. 6-Chloropurine was oxidized with monoperphthalic acid in ether to give 6-chloropurine 3-N-oxide. These purine 3-N-oxides were then converted to hypoxanthine 3-N-oxide by hydrolysis with a sodium hydroxide solution. 6-Methoxypurine 3-N-oxide and hypoxanthine 3-N-oxide were identified with authentic samples unambiguously synthesized from 6-methylsulfonylpurine 3-N-oxide, which had itself been obtained by the oxidation of 6-methylthiopurine 3-N-oxide. The treatment of hypoxanthine 3-N-oxide with hydrochloric acid gave 6,8-dihydroxypurine, 8-chlorohypoxanthine, hypoxanthine, and 2-chloro-4-amino-5-imidazolecarboxamide.
Polymerization of Naphthalene and Reactions of Polynaphthalene
Authors: Minato Hiroshi , Higosaki Nobuyuki , Isobe Chieko
Published: July 2006

Naphthalene was polymerized by use of anhydrous aluminum chloride. The polynaphthalene formed was soluble in various organic solvents. The molecular weight determination suggested that the average degree of polymerization was six. The NMR spectrum indicated the presence of non-aromatic hydrogens, and the elemental analysis roughly corresponded with (C10H8)n. The reactions of the polymer was examined such as hydrogenation, bromination, thermal dehydrogenation, chloromethylation and epoxidation.
The Wolff Rearrangement. V. Kinetic Isotope Effect of α-Diazoacetophenone
Authors: Yukawa Yasuhide , Ibata Toshikazu
Published: July 2006

Kinetic isotope effect of the Wolff rearrangement of carbonyl-14C and phenyl-1-14C labeled α-diazoacetophenone was measured in t-butyl alcohol at 30°C, using a solution of silver benzoate in triethylamine as a catalyst. No apparent kinetic isotope effect was observed in both cases within experimental error. These results suggest that the elimination of nitrogen and the migration of phenyl group proceed in two steps in the rate-determining step.
Thermodynamic Properties of Neopentane from 4°K to the Melting Point and Comparison with Spectroscopic Data
Authors: Enokido Hisae , Shinoda Takako , Mashiko Yo-ichiro
Published: July 2006

Heat capacities, latent heats and vapor pressures of solid and liquid neopentane were measured and the following values were obtained; heat of transition=628.7±0.3 cal/mol, T(trans. pt.)=140.498±0.05°K, heat of fusion=740.0±0.3 cal/mol, T(triple pt.)=256.750°K, and P(triple pt.)=268.47±0.13 Torr. The amount of impurity in the sample after purification was estimated from a plot of the equilibrium temperature against the reciprocal of the fraction melted. From the result the impurity present was found to be 0.0032 mol%. Despite of high purity, Cp value in the region below the melting point increases unexpectedly with temperature. This is interpreted as an effect of formation of vacancies in the crystals. The enthalpy required to form vacancies was estimated to be 3240±220 cal/mol from the analysis of the heat capacity curve in the region below the melting point. The molal entropy of the ideal gas at the boiling point, calculated from the calorimetric data, was 71.24±0.3 e. u. To bring this value into agreement with the value calculated from the infrared and Raman frequencies and the moments of inertia, requires the assumption of three equal potential energy maxima of 4.4 kcal/mol for hindered internal rotation of the methyl groups.
Effect of Potassium Promoter on Iron Oxide Catalysts for Dehydrogenation of Ethylbenzene to Styrene
Authors: Shibata Katsue , Kiyoura Tadamitsu
Published: July 2006

The catalytic activity and the sintering property of iron oxide catalysts with and without potassium additives have been studied. The potassium oxide acts as a promoter and is effective under given conditions in increasing the activity of the catalyst from four to ten times. The effects of the promoter can be classified thus: (1) Structural promoter: The increase in the apparent bulk density and the shrinkage of the catalyst tablet upon calcination during the preparation of the catalyst are prevented by potassium additives. The differences in the specific surface area and in the pore volume of the catalyst between with and without potassium promoter are slight. These effects on iron oxide appear to be caused largely by the formation of K2Fe22O34. (2) Synergetic promoter: The potassium promoter changes the apparent energy of activation of the dehydrogenation reaction from 28 to 43 kcal/mol. The increase in the catalytic activity is due to the increase in the pre-exponential factor. The increase in the factor can be explained in terms of the higher concentration of the active center produced by the interaction of the potassium promoter with iron oxide. (3) Selectivity promoter: The formation of benzene by a side reaction is retarded by potassium additives.
The Crystal and Molecular Structure of Bis-(N,N′-π-cyclopentadienyl cobalt)-di-tert-butyl Urea, (π-C5H5Co)2(N,t-C4H9)2CO
Authors: Matsuura Yoshiki , Yasuoka Noritake , Ueki Tatzuo , Kasai Nobutami , Kakudo Masao
Published: July 2006

The crystals of (π-C5H5Co)2(N-t-C4H9)2CO are orthorhombic, and the space group is Fdd2, with a=9.101, b=17.973, c=23.616 Å, and Z=8. The crystal structure was determined with use of MoKα counter data, the final R being 0.063 for 578 non-zero reflections. The molecules has a C2 symmetry, and the carbonyl group lies exactly on the two-fold axis. Unexpectedly, the molecule has the local structure of N,N′-di-t-huty urea, two nitrogen atoms being bridged to two cobalt atoms. The two crystallographically independent Co-N bonds are 1.942 and 1.951 Å, which are equal within the limits of experimental error. Two cobalt atoms are directly bonded to each other at a distance of 2.371 Å, which is shorter than that of 2.47 Å found in (CO)6Co2(C2Ph2).
The Crystal Structure of Two Crystalline Polymorphs of N-(p-Methoxy phenyl-3-propyl)-p-bromobenzamide
Authors: Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The crystal structure analysis of N-(p-methoxyphenyl-3-propyl)-p-bromobenzamide was carried out by means of X-rays. This compound crystallizes in two crystalline polymorphs, both belonging to the monoclinic system.

α-form:a=14.592,b=9.572,c=11.242Å,β=94.26°;Z=4;space groupP21c

β-form:a=11.940,b=10.019,c=6.577Å,β=90.56°;Z=2;space groupP21.

A little difference in structure is observed between the molecules in the two polymorphs, while the conformations of the carbon-carbon bonds in the 3-aminopropyl group are of the trans form. In both forms, belts of molecules parallel to the b axis are formed by hydrogen bonds between the amide groups of the molecules related by the twofold screw axis. These belts are packed anti-parallel in the α-form, but parallel in the β-form.
The Electronic Structures of Unstable Intermediates. Benzyne and Hetarynes
Authors: Yonezawa Teijiro , Konishi Hideyuki , Kato Hiroshi
Published: July 2006

A semi-empirical SCF MO method for valence electron systems, a modification of our previous method made by introducing the zero-differential overlap approximation except for the one-center exchange integrals, is presented. The results calculated for benzene, pyridine, pyrimidine and thiophene, the parent molecules of benzyne and hetarynes, using this modified method are compared with those obtained by the other calculations and experiments. The unstable intermediates treated in the present paper are benzyne, pyridynes, pyrimidyne and thiophynes. The unknown bond lengths of benzyne and hetarynes are estimated by a semi-empirical relation given in the present treatment. The nature of the carbon-carbon triplet bonds of benzyne and hetarynes is studied on the basis of the bond lengths and the total π bond orders for these bonds. The charge distributions and excitation energies of benzyne and hetarynes, and the chemical reactivity of some hetarynes are also discussed. The lowest triplet states of these intermediates are shown to be close to the singlet ground states.
The Yields of Photonuclear Reactions Leading to the Production of Beryllium-7 with Bremsstrahlung up to 60 MeV
Authors: Oka Yoshinaga , Kato Toyoaki , Yamadera Akira
Published: July 2006

Beryllium, boron, carbon, oxygen, and fluorine targets with natural isotopic compositions were irradiated by bremsstrahlung with four maximum energies, 30, 45, 55 and 60 MeV, and the yields of 7Be from each of these targets were determined by means of chemical separation and gamma-ray spectrometric measurements. The yields were obtained relative to the yield of the 12C(γ, n)11C reaction at each bremsstrahlung energy. The possible reaction pathways leading to the production of 7Be were discussed. The exponential decrease in the yield value against the difference in mass between the target and the product nuclei was observed.
Cobalt(IV) Ammine Complexes with 5-Nitrosalicylato or Similar Ligands. II. Preparation and Properties of Derivatives
Authors: Yamamoto Yoshihisa , Mori Masayasu , Yoneda Hayami , Misumi Soichi , Ito Kazuo
Published: July 2006

Cobalt(IV) compounds of the formulae: (Remark: Graphics omitted.) have been obtained by procedures analogous to that reported for cobalt(IV) ammine complexes with 5-nitrosalicylato ligands.
The Solvent Extraction of Metal Ions from Sulfuric Acid Solutions with a Mixed Extractant—Long-chain Primary Amine and Di-2-ethylhexylphosphoric Acid
Authors: Watanabe Hiroto
Published: July 2006

The distribution of metal ions between phases of dilute sulfuric acid and carbon tetrachloride containing long-chain primary amine (Primene JM) and di-2-ethylhexylphosphoric acid (D2EHPA) has been investigated. The degree of the extraction of bi- and tervalent metal ions, such as zinc, iron (III), indium, lanthanum, and cerium(III), is found to be the lowest when the organic phase contains 5 g/l of Primene JM and 7–8 g/l of D2EHPA, while a minimum extraction of thorium occurs at a different composition of the organic phase. Thus, thorium can be quantitatively separated from most other metals by extraction from a 0.1n sulfuric acid medium with carbon tetrachloride containing 5 g/l of Primene JM and 7–8 g/l of D2EHPA. Under these extraction conditions, a single extraction is sufficient for the quantitative separation of thorium from high concentrations of lanthanide metals. Contrary to the usual method of extraction using long-chain amines, which involves a tedious multiple extraction, the mixed-extractant technique described is simple and will find many uses in the determinations of thorium in a variety of samples.
Solvent Effects on the g Factors of Semiquinones
Authors: Yonezawa Teijiro , Kawamura Takashi , Ushio Masaru , Nakao Yukimichi
Published: July 2006

The dependence of the g factors of p-benzosemiquinone and its tetrahalogenated derivatives on the solvent composition has been studied in the dimethyl sulfoxide-water system. When the water content of the solvent increases, the g factor of p-benzosemiquinone decreases, that of tetrachloro-p-benzosemiquinone scarcely changes, and the g factors of tetrabromo- and tetraiodo-p-benzosemiquinones increase. These phenomena are interpreted qualitatively by assuming that the water molecule solvates to the carbonyl oxygen atom of semiquinones and by using Stoned equation for the g factor of the polyatomic radical. The dependence of the g factor of p-benzosemiquinone on the solvent composition is quantitatively studied by means of the theory of solvent effects proposed by Gendell, Freed and Fraenkel and by using the 2-site model of Stone and Maki and also the 4-site model. The former model assumes that one carbonyl oxygen atom has one site occupied by a solvent molecule, thus resulting in a dominant g shift. In the later model, two solvent molecules interact with one carbonyl oxygen atom. Both models predict the same relation between the g shift and the solvent composition; this experiment cannot confirm which model is more adequate, although the deduced values of the equilibrium constants indicate that the 4-site model is preferable.
Verification of the Conduction Method in Calorimetry
Authors: Tanaka Satohiro , Amaya Kazuo
Published: July 2006

An ideal three-dimensional model of a conduction calorimeter is presented. In the model, the heat transfer takes place only by conduction. The proportionality relation between the quantity of heat and the area enclosed by the recorded temperature curve and the time axis is proved under several sets of ideal conditions under which the proportionality relation is valid are examined, and thermal compensation is recommended for more precise measurements of heat and for convenience in obtaining thermogenesis curves.
The Crystal and Molecular Structure of Bis(2-hydroxyethylimino-salicylaldehydato)copper(II)
Authors: Iijima Kinya , Oonishi Isao , Muto Fumio , Nakahara Akitsugu , Komiyama Yoshimichi
Published: July 2006

The crystal structure of bis(2-hydroxyethyliminosalicylaldehydato)copper(II) has been determined by means of an X-ray diffraction study of a single-crystal specimen. Four formula units are contained in the monoclinic unit cell, the P21⁄c space group, with lattice parameters of: a=18.41 A, b=4.82 Å, c=19.86 Å, and β=99.1° (Dm=1.50 g·cm−3; Dx=1.50 g·cm−3). The structure has been refined, by means of three-dimensional difference syntheses and the least-squares method, to R=0.095. It has been confirmed that copper(II) links to the 2-hydroxyethyliminopyruvate anion through the phenolic oxygen and the nitrogen of the Schiff base linkage, while the alcoholic oxygen in the ethanol-amine moiety is free from coordination. The two Schiff-base ligands are coordinated around copper(II) in the trans-configuration. All the bond distances and angles in the complex are within the range of normal values. The N-Cu-O angles (91.3 and 91.8°) in the chelate rings are close to a right angle, showing that there is less strain in the chelate structure than in the case of a similar chelate of the pyruvate Schiff base (84.6°).
Mössbauer Studies of the Thermal Decomposition of Iron(II) Pyridine and Picoline Complexes
Authors: Tominaga Takeshi , Takeda Masuo , Morimoto Takeshi , Saito Nobufusa
Published: July 2006

The thermal decomposition of tetrakispyridineiron(II) chloride, tetrakis(γ-picoline)iron(II) chloride, and tetrakispyridineiron(II) isothiocyanate has been studied in nitrogen. These complexes presumably decompose in the following sequences:

Fe(py)4Cl2 → Fe(py)2Cl2 → Fe(py)Cl2 → Fe(py)2⁄3Cl2 → FeCl2,

Fe(γ-pic)4Cl2 → Fe(γ-pic)Cl2 → FeCl2 and Fe(py)4(NCS)2 → Fe(py)2(NCS)2 → Fe(NCS)2.

The Mössbauer spectra of these complexes and of their decomposition products have been studied in terms of the structural change about the iron atom during the thermal decomposition process.
Reaction of Olefin-Palladium(II) Chloride Complexes with n-Butylamine
Authors: Hirai Hidefumi , Sawai Hiroaki , Makishima Shoji
Published: July 2006

Olefin-palladium(II) chloride complexes reacted with n-butylamine to form Schiff’s bases. N-Ethylidene-n-butylamine was obtained by the reaction of the ethylene complex with n-butylamine, accompanied by reduction of palladium(II) to the metal. A tris(n-butylamine)palladium chloride complex was formed simultaneously by ligand substitution reaction. The yield of N-ethylidene n-butylamine was 15–19mol% (calcd on palladium) in 2.5 hr at 25°C, and decreased at temperatures higher than 60 °C with increasing reduction of palladium(II), owing to conversion of N-ethylidene-n-butylamine into either N-crotylidene-n-butylamine or a tarry polymeric substance by aldol type condensation reaction. The n-butylamine-palladium(II) chloride complex did not react with ethylene at 25°C, but reacted with ethylene at 150°C to form a large amount of tarry polymer and a small amounts of N-ethylidene-n-butylamine and N-crotylidene-n-butylamine. The propylene complex and the cyclohexene complex reacted with n-butylamine to yield both 2- and 1-N-propylidene n-butylamine, and N-cyclohexylidene-n-butylamine respectively. The yield of Schiff’s bases from olefin complex decreased in the order, ethylene>propylene>>cyclohexene.
Scrambling of Oxygen in the Diester Produced from Labeled Diacyl Peroxide-Olefin Reaction
Authors: Kobayashi Michio , Minato Hiroshi , Ogi Yoshikuni
Published: July 2006

dl-Dihydroanisoin bis-m-bromobenzoate produced from the reaction between p,p′-dimethoxy-trans-stilbene and m,m′-dibromobenzoyl peroxide labeled with oxygen-18 at the carbonyl oxygen was found to possess completely equilibrated oxygens, and this finding indicated that a four-centerd mechanism was unlikely.
The Reaction of Sulfenyl Chlorides with Thioethers. I. The Scope of the Reactions
Authors: Oki Michinori , Kobayashi Keiji
Published: July 2006

It was found that thioethers reacted with sulfenyl chlorides to give four kinds of products. When the alkyl part of the thioether is capable of producing a rather stable carbonium ion, the thioether gives the chloride and an olefin, which are derived from the cation, the latter reacting also with the sulfenyl chloride to give adducts. There is another path to afford alkyl chloride; that is, an SN2-type reaction takes place when the alkyl part gives a less stable carbonium ion. The third and fourth products are α-chloro sulfide and α,β-unsaturated sulfide, which are seemingly produced via a common intermediate. The latter may react further with the sulfenyl chloride to give enedithiol derivatives.
Determination of Magnetic Moments of Copper Ions in Water by the Viscometer Method
Authors: Ikeda Toshio , Sueoka Kazuo
Published: July 2006

The viscometer method was applied to determine the magnetic susceptibilities of aqueous solutions of cupric salts. The effective magnetic moments of the cupric ions obtained were in agreement with values in literature, except for cupric nitrate and acetate. The former showed a relatively high value and the latter gave variable values, which suggest some dimerization effect occuring in aqueous solution with increasing concentration.
The Cadmium-photosensitized Decomposition of Acetone
Authors: Sato Shin , Takahashi Chiharu , Tsunashima Shigeru
Published: July 2006

The cadmium-photosensitized decomposition of acetone has been studied and compared with the 3261 Å direct photolysis at 270±1°C. The data could be consistently explained by the following reaction mechanism:

& Cd(^3P_1)+CH_3COCH_3→Cd+^3A^*\labeleq1

& ^3A^*→2CH_3+CO\labeleq2

& CH_3+CH_3COCH_3→CH_4+CH_3COCH_2\labeleq3

& 2CH_3→C_2H_6\labeleq4

& CH_3+CH_3COCH_2→C_2H_5COCH_3\labeleq5

& 2CH_3COCH_3→(CH_3COCH_2)_2\labeleq6

The mechanism from (2) to (6) is exactly the same as that proposed for the 3130 Å direct photolysis at temperatures higher than 100°C. By using the cis-trans isomerization of 2-butene as the actinometer, the quantum yield of the photosensitized decomposition of acetone was estimated to be 0.3. Kinetic analysis showed that the energy-rich ethane produced by the recombination reaction (4) has the lifetime of 2×10−8 sec at 270°C.
The Crystal Structure of trans-Dinitratobis(trimethylenediamine)-cobalt(III) Nitrate
Authors: Yasaki Eeki , Oonishi Isao , Kawaguchi Hiroshi , Kawaguchi Shinichi , Komiyama Yoshimichi
Published: July 2006

The crystal structure of trans-[Co(NO3)2(tn)2]NO3 (tn: H2N–CH2–CH2–CH2–NH2) has been determined from three-dimensional X-ray diffraction data. The dimensions of the monoclinic unit cell are: a=8.62 Å, b=10.04 Å, c=9.61 Å, β=114.0°, and Z=2. The space group is P21/c. The structure has been refined by the least-squares method to R=0.114. The complex ion has a slightly distorted octahedral coordination, with four N atoms of trimethylenediamine molecules at 1.990±0.009 Å and two O atoms of nitrate ions at 1.898±0.007 Å. The two six-membered cobalttrimethylenediamine rings are identical, as is required by the center of symmetry, and take the chair form. The complex ions and nitrate ions are tightly bound together by N–H···O hydrogen bonds in the layers parallel to the (100) plane, but there exists no evidence for hydrogen bonding between the layers.
Measurement of the Lyonium Ion Concentration in a H2O-D2O Mixed Solvent by Means of a Glass Electrode
Authors: Kakihana Hidetake , Maeda Masunobu , Amaya Toshihiko
Published: July 2006

In the present work, experiments were carried out for the systems of 20, 80 and 99.8% heavy water. It has turned out that the relationship between the emf and the lyonium ion concentration in a H2O–D2O mixed solvent can be expressed at 25°C by the so-called Nernst equation within the limits of experimental accuracy of ±0.1 mV. This means that the lyonium ion concentration in a H2O–D2O mixed solvent can be measured with the same experimental accuracy (uncertainty of ±0.1 mV) as that in light water by the use of a glass electrode.
Bis-Type Cobalt(III) and Chromium(III) Complexes with Related Compounds of Nitrilotriacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

β-Amino-n-butyric-N,N-diacetic acid (β-ABDA) and γ-amino-n-butyric-N,N-diacetic acid (γ-ABDA) were prepared as compounds related to nitrilotriacetic acid (NTA). Bis-type cobalt(III) and chromium(III) complexes with these ligands, viz., K3[Co(β-abda)2] (I), K[Co(H-γ-abda)2]·2H2O (II) and K[Cr(H-γ-abda)2]·2H2O (III), and the same type cobalt(III) complex with β-aminoethylsulfonic-N,N-diacetic acid (AEDA), viz., K3[Co(aeda)2]·4H2O (IV), were also synthesized. Chemical properties of the above complexes were compared with those of the chromium (III) complex corresponding to IV and of the cobalt(III) and chromium(III) complexes with NTA and NPDA. From the analysis of electronic spectra, it was found that the new complexes, I, II, III and IV have the trans form with respect to the nitrogn atoms in the ligands. A spectrochemical series of these ligands, containing iminodiacetic acid (IDA), methylimino-diacetic acid (MDA) and ethyliminodiacetic acid (EDA), was determined to be:

IDA>MDA>NPDA>β-ABDA>EDA>AEDA>NTA>γ-ABDA.
Chlorinative Coupling of Thiophene by the Action of Sulfuryl Chloride and Iron Powder
Authors: Sone Tyo , Sakai Koji , Kuroda Kimio
Published: July 2006

In the presence of iron powder, thiophene reacted with sulfuryl chloride at room temperature to give a mixture of chlorinated 2,2′-dithienyls as the main product in yields of up to 42%, while the reaction without a catalyst gave chlorothiophenes. The yield of the coupling product and the chlorine content in the product increase with an increase in the molar ratio of sulfuryl chloride to thiophene. 5,5′-Dichloro-, 3,5,5′-trichloro-, and 3,3′,5,5′-tetrachloro-2,2′-dithienyls were isolated from the reaction products. The reaction was also catalysed by Friedel-Crafts-type catalysts, the efficiency of the catalysts decreasing in the order: AlCl3>FeCl3>SnCl4>ZnCl2.
Reaction of Sulfoxides with Acylating Reagents. I. Mechanism of Oxygen Exchange Reaction of Diaryl Sulfoxides with Acetic Anhydride
Authors: Oae Shigeru , Kise Masahiro
Published: July 2006

Racemization and oxygen exchange reactions were carried out by heating both optically active and 18O-labeled diaryl sulfoxides in a large excess of acetic anhydride. The rate of racemization of p-tolyl phenyl sulfoxide was found to be twice the rate of oxygen exchange, suggesting the reaction to involve a Walden inversion at the rate-determining step. When the reaction was carried out in a mixture of acetic anhydride and chlorobenzene, the rate of racemization was found to be first order with respect to both the sulfoxide and acetic anhydride. The remarkably small substituent effect is also in keeping with the SN2 type mechanism. The marked retardation of the rate of racemization by the addition of common salt is similar to well-known cases in the SN2 reaction of alkyl halides, and the remarkably large acceleration of the rates of both racemization and oxygen exchange reactions by the addition of sodium perchlorate seems to be caused by a special salt effect.
Reaction of Sulfoxides with Acylating Reagents. II. Mechanism of the Reactions of Aryl Benzyl Sulf oxides with Acetic Anhydride
Authors: Kise Masahiro , Oae Shigeru
Published: July 2006

Aryl benzyl sulfoxides undergo oxygen exchange and racemization reaction with acetic anhydride, and the rate is dependent on the concentration of both the sulfoxide and acetic anhydride. The reaction proceeds faster in a more polar solvent. Addition of sodium perchlorate or acetic acid accelerates the reaction. In this case, the rate of oxygen exchange is not exactly half of that of racemization. As an example, the ratio, kex/krac, is 0.36 when the reaction was carried out at 100°C. Under the same condition, both the Pummerer reaction and thermal racemization are negligible. Similar to diaryl sulfoxides the effects of phenyl group are small. Implication of the ratio is discussed.
The Reaction of Cadalene and Eudalene with Sulfur
Authors: Kurokawa Shinji
Published: July 2006

The action of sulfur on two naphthalenes was investigated. Cadalene was heated with sulfur to give a new sulfur-containing naphthalene, 1,5,8-trimethylnaphtho[2,1-b] thiophene. It was formylated at the C2-position of the thiophene moiety according to the Vilsmeier procedure, while an attempted acetylation according to this procedure was unsuccessful. Similarly, the reaction of eudalene with sulfur gave 3,9-dimethylnaphtho[1,2-b]thiophene, whose structure was determined by chromium trioxide oxidation, yielding o-quinone, and by a subsequent reaction with o-phenylenediamine, forming a quinoxaline derivative.
New Method for the Separation of Diastereomeric Mixtures of β-Methylnorleucine and β-Methylleucine
Authors: Okubo Kazuo , Izumi Yoshiharu
Published: July 2006

β-Methylnorleucine and β-methylleucine were synthesized, separated into diastereomers and optically resolved. The configurational assignments of these isomers and the determinations of the optically active isomers were achieved by means of NMR spectroscopy and the enzymatic method respectively.
The Retentive Solvolysis. VII. Structural Effect of the Leaving Group on the Steric Course of the Sn1 Phenolysis of 1-Phenylethyl Systems
Authors: Okamoto Kunio , Kinoshita Tomomi , Shingu Haruo
Published: July 2006

A series of optically active 1-phenylethyl systems with various leaving groups has been phenolyzed in the phenolic solvents. The 1-phenylethyl systems with a negative leaving group (i.e., 1-phenylethyl chloride, bromide, 3,5-dinitrobenzoate, and tosylate) afforded 1-phenylethyl phenyl ether with a net retained configuration. In contrast, the 1-phenylethyl systems with a positively-charged leaving group (i.e., the 1-phenylethyldiazonium ion, the diethyl-(1-phenylethyl)-oxonium ion, and the protonated 2,6-di-t-butyl-4-methyl-4-(l-phenylethyl)-cyclohexadien-l-one) .gave the 1-phenylethyl phenyl ether with a net inverted configuration. These results provide further support for the view that the retentive Sn1 phenolysis proceeds via a four-center transition state between the phenol molecule and the ion-pair intermediate. Besides the phenolic ether, the o- and p-(1-phenylethyl)-phenols with net inverted configurations were obtained from all optically active substrates except 1-phenylethyl 3,5-dinitrobenzoate and the 1-phenylethyldiazonium ion. The 3,5-dinitrobenzoate gave the completely racemic o-alkylated phenol, along with the inverted p-alkylated phenol, whereas the diazonium ion afforded the o-alkylated phenol with a net retained configuration, together with the inverted p-alkylated phenol. The stereochemical and mechanistic implications of the C-alkylation are also discussed on the basis of the results of the acidic rearrangement of the phenolic ether under the Sn1 phenolysis conditions.
Redox Reactions on the Lithiated Nickel Oxide Electrode
Authors: Yoneyama Hiroshi , Tamura Hideo
Published: July 2006

The redox reactions of the Ce3+/Ce4+, Fe2+/Fe3+ and Fe(CN)64−/Fe(CN)63− systems on lithiated nickel oxide electrodes in a H2SO4 medium were studied. For the Fe2+/Fe3+ and Fe(CN)64−/Fe(CN)63− systems, the reactions were controlled by an activation process when the electrode was polarized anodically, while the current tended to saturation as the current was increased in the cathodic direction. The apparent exchange current densities of these systems were distinctly dependent on the resistivity of the electrode. These phenomena were discussed qualitatively from a consideration of the energy states of the charge carriers in the electrode and redox systems, and it was concluded that all the reactions had proceeded through only hole transfer.