bluuebunny/crossref_metadata_2025 huggingface dataset:
The Oligomerization of Butadiene with Iron Complex Catalysts. II. The Effects of Additives
Authors: Hidai Masanobu , Tamai Katsumi , Uchida Yasuzo , Misono Akira
Published: July 2006

In the oligomerization of butadiene with the catalyst composed of iron(III) acetylacetonate and triethylaluminum, the degree of digomerization and the structures of the oligomers were strongly affected by the addition of an electron donor as a catalyst component. When triphenylphosphine was added, linear dimers composed of 3-methylhepta-1, 4, 6-triene and n-octa-1, 3, 6-triene were formed, while the addition of 2, 2′-dipyridyl produced cyclic dimers composed of cycloocta-1, 5-diene and 4-vinylcyclohex-1-ene. Besides the above donors, triphenylphosphite, tri(o-tolyl)-phosphite, tri(p-tolyl)phosphite, phosphorus trichloride, triethylamine and pyridine as monodentate, and o-phenanthroline, 2(2′-pyridyl)imidazoline and oxine as bidentate ligands, were tried, and the effects of those donors upon the reaction were studied. The transition states in these catalyst systems were also considered by means of studies of the effects of the molar ratio of catalyst components and by the measurements of infrared, ESR and visible light absorption spectra or magnetic susceptibilities of the reaction solutions.
The Electronic Structures of Hydrides, Halides and Alkyl Compounds of Boron and Aluminum. II. Dimers
Authors: Kato Hiroshi , Yamaguchi Kaichiro , Yonezawa Teijiro
Published: July 2006

The electronic structures of dimers containing boron and aluminum atoms, i. e., B2H6, B2H2-(CH3)4, Al2Cl6, Al2Cl2(CH3)4 and Al2(CH3)6, are investigated by an extended Huckel method. The calculations show that the central linkages are weak and that their bonding natures are very different from those of the bonds between the metals and terminal atoms. Judging from the orbital energies and populations, these dimers still hold a strong acidity, like that in the monomers, an acidity which depends mainly on the existence of the almost unfilled pπ orbitals of the metal atoms, where the electrons occupying the lower vacant orbitals in these dimers are almost localized. The results are compared with other calculations and experimental results. It is, further, shown by examining the electronic structures of two hypothetical compounds that these dimers can be easily formed by using the vacant valence orbitals of the metal atoms, and that the metal-metal bonds in some dimers are considerably strong.
On the Carbon-13 Chemical Shifts of Saturated Hydrocarbons
Authors: Yonezawa Teijiro , Morishima Isao , Kato Hiroshi
Published: July 2006

A molecular orbital interpretation of the carbon-13 chemical shifts of saturated hydrocarbons is presented. The shielding constant of the carbon atom is shown to be roughly proportional to the excess charge densities of 2p electrons, which is in accordance with experiments. The so-called β- and γ-effects in the carbon-13 chemical shifts are explained on the basis of an MO theory.
Vibrational Frequencies and Normal Coordinates: Their Relationship to Force Constants and Inertial Coefficients
Authors: Miyazawa Tatsuo , Overend John
Published: July 2006

Small variations in the G and F matrices can be related linearly to variations in the calculated frequencies and normal coordinates through a transformation matrix, J. Explicit expressions are given for the elements of J and J−1. Isotope effects on normal-coordinate coefficients are also treated.
The Effect of Oxygen on the Semiconductivity of Quaterrylene
Authors: Maruyama Yusei , Inokuchi Hiroo
Published: July 2006

The electrical conductivity of an evaporated film of quaterrylene varied with the pressure of the ambient oxygen. The resistivity was 1.1×1012 Ωcm. in a vacuum of 4×10−8 mmHg; this was very large compared with the previously-reported value, ∼106Ωcm., which was obtained after exposing the film to the air of an atmospheric pressure. The temperature dependence of the resistance of the film was also affected by the ambient oxygen. The intrinsic semiconductor model could be applied only in the case of a high vacuum (∼10−8 mmHg); the band gap, Δε, was 1.7 eV. in this case. From the resistance-temperature relations at the various oxygen pressures, it seems that two acceptor levels, 0.03 eV. and 0.6 eV. above the valence band respectively, exist.
A Study of the Pyrolysis of Toluene Using 14C as a Tracer
Authors: Takeuchi Toyosaburo , Sakaguchi Masakazu , Togashi Yoshio
Published: July 2006

The pyrolysis of toluene-1-14C was carried out by means of the semi-flow method at 800 and at 1000°C in the presence of the registers of porcelain, and the distributions of the radioactive carbon in gaseous products and that of the deposited carbon were determined. The molar c.p.m. of methane and that of a mixture of C2-compounds were about 1/20 of and twice the molar c.p.m. of the original toluene respectively, while the c.p.m. per gram-atom of the deposited carbon was about twice that of toluene, when the temperature of reaction was 800°C. In the case of the reaction at 1000°C, the c.p.m. per gram-atom of carbon of each product was found to be practically equal to that of the original toluene. It was proposed that methane is formed by the removal of the methyl group of toluene, and that the main source of the carbon of C2-compounds and the deposited carbon is the 1-carbon of toluene. The equalization of the radioactive carbon in every product at a high temperature was interpreted by assuming that the tropyl radical is formed as an intermediate after the formation of the phenyl radical in the initial stage of the reaction.
Studies of the Organic Reaction of Metal Carbonyl. VIII. The Isomerization of Aliphatic C5- and C6-Acylcobalt Carbonyls
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Masada Hiromitsu , Okuda Yasukazu , Kubo Keiji , Yokokawa Chikao
Published: July 2006

The isomerization of C5-acyl(n-valeryl- and α-methylbutyryl-) and C6-acyl(n-caproyl-, α-methylvaleryl- and α-ethylbutyryl-) cobalt carbonyls has been studied and compared with that of C4- acyl(n- and isobutyryl-) cobalt carbonyls previously reported. It has been observed that solvents have great effects on the isomerization (the rate and equilibrium) of the C5-acylcobalt carbonyls. The equilibrium proportion of the isomers (iso/normal) is almost 1 in diethyl ether and tetrahydrofuran. In solvents such as dioxane, ethyl acetate and benzene it seems difficult for this isomerization to occur. α-Ethylbutyrylcobalt carbonyl appears to isomerize directly to n-caproylcobalt carbonyl. However, n-caproylcobalt carbonyl isomerizes only to α-methylvaleryl-cobalt carbonyl; the reverse isomerization also occurs, but it seems very difficult for any other isomerization between the two of them to occur.
Synthetic Studies starting from β-Cyanopropionaldehyde. III. The Synthesis of β-Cyanoacrolein
Authors: Motoki Shinichi , Satsumabayashi Sadayoshi , Masuda Takashi
Published: July 2006

β-Cyanopropionaldehyde dimethyl acetal was brominated in the presence of calcium carbonate to give α-bromo-β-cyanopropionaldehyde dimethyl acetal. This was then dehydro-brominated with 10% alcoholic potash at −5 to 0°C, β-cyanoacrolein dimethyl acetal was thus obtained in a high yield. Free aldehyde of a light green liquid was given by the hydrolysis of the acetal. A similar procedure using α-chloro-β-cyanopropionaldehyde dimethyl acetal was also examined. On the other hand, β-cyanoacrolein was prepared by the direct dehydro-genation of β-cyanopropionaldehyde with selenium dioxide.
Sophorol
Authors: Suginome Hiroshi
Published: July 2006

The structure of sophorol was confirmed to be 2′:7-dihydroxy-4′:5′-methylenedioxyisoflavanone by the synthesis of dehydro-O-dimethylsophorol, 2′:7-dimethoxy-4′:5′-methylenedioxyisoflavone.
Plastic Scintillators. III. The Synthesis of Some Anthracene Derivatives as Wavelength Shifters in Plastic Scintillators
Authors: Nakaya Tadao , Tomomoto Takanori , Imoto Minoru
Published: July 2006

Fifteen anthracene derivatives have been synthesized, and their absorption and fluorescence spectra have been measured. The spectra will be discussed in this paper. According to the spectra, some of anthracene derivatives synthesized here are better wavelength shifters than the compounds previously described in the literature.
Nitrous Oxide as an Electron Scavenger in the Radiolysis of Hydrocarbons
Authors: Sato Shin , Yugeta Rei , Shinsaka Kyoji , Terao Terumi
Published: July 2006

Nitrous oxide has been used as an electron scavenger in the radiolysis of hydrocarbons: cyclohexane, cyclohexene, benzene, and their mixtures. Considering that the energy for the formation of an ion pair is about 25 eV. in hydrocarbons, 0.4mol.1−1 of nitrous oxide is not enough to capture all the electrons ejected from irradiated hydrocarbons. In the case of cyclohexane, 70% of the ejected electrons seem to be captured by 0.4mol.1−1 of nitrous oxide. In the case of benzene, G(N2) is about a half of that for cyclohexane. This has been explained tentatively in terms of the ability of benzene to capture electrons. The G(N2)’s in the cases of cyclohexene and benzene have not shown any noticeable dependence on the concentration of nitrous oxide. This shows that hydrogen does not result from the neutralization in these systems. In order to clarify them, the primary processes in the radiolysis of cyclohexane have been further considered using the data previously obtained.
The Trifluoroacetate Method of Peptide Synthesis. II. An Improved Synthesis of Bradykinin
Authors: Sakakibara Shumpei , Inukai Noriyoshi
Published: July 2006

When p-nitrophenyl trifluoroacetate (I), 2, 4, 5-trichlorophenyl trifluoroacetate (II) and N-hydroxysuccinimide trifluoroacetate (III) were subjected to Anderson’s racemization test, only reagent III showed resistance against racemization. However, reagents I and II were also found to be useful for fragment-condensation with acylpeptides possessing glycine or proline at the C-terminus. Bradykinin was prepared using these reagents. During the synthesis, a combination of the t-amyloxycarbonyl N-protecting group and the benzyl ester was mainly used, and the alkaline hydrolysis procedure of the ester group was eliminated. Thus, colorless bradykinin with full activity was obtained in a satisfactory yield without any purification procedure.
The Radiolysis of a Binary Mixture of Tetrahydrofuran with Furan
Authors: Matsui Masao
Published: July 2006

The radiolysis of a tetrahydrofuran(THF) and furan system was studied at a dose of about 2×1019 eV. ml−1 of 60Co-γ-rays, and the hydrogen which may be formed by the no-ring opening and the carbon monoxide which should be formed by the ring scission were determined. The decrease in the hydrogen yield with an increase fraction of furan was found to be greater than had been expected, while G(CO) fit the expected value. The charge transfer mechanism was presumed for the decrease in the hydrogen yield in the γ-radiolysis of this mixture. Suggestions were made on the probable mechanism of the ring opening of the excited molecule for the formation of carbon monoxide, and on the ionic reaction for hydrogen formation. Furthermore, the probability of the ring scission of the THF molecule was roughly estimated by using the assumed decomposition reaction and the determined G values.
Sensitization in the Photoconductance of Poly-N-vinylcarbazole
Authors: Hayashi Yoshiki , Kuroda Makoto , Inami Akira
Published: July 2006

The sensitization in photoconductive poly-N-vinylcarbazole was studied systematically. The sensitizers were conveniently divided into two types, optical and chemical. The optical sensitization occurs with a smaller content of a dye, which extends the photoconductivity spectrum to its absorption band. Effective optical (or dye) sensitizers are found to be themselves photoconductive and n-type cationic and to have a slow photoresponse. The chemical sensitization occurs through the formation of a charge transfer complex with a considerable amount of a Lewis acid. The simultaneous addition of optical and chemical sensitizers induces amplified or additive effects; an amplified effect is observed when a strong acid is employed as a chemical sensitizer. A sensitized system with a strong acid shows a very slow photoresponse and may have fairly deep traps which act as a cause of the memory effect.
Studies of Mixed Cyano Cobalt(III) Complexes. II. The Geometrical Isomers of [CoX(CN)en2]+
Authors: Ohkawa Kuwako , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Two new mixed cyano complexes, cis-[CoCl(CN)en2]Cl (red) and cis-[CoBr(CN)en2]Br (deep rose), have been synthesized and resolved into their optical isomers. The splitting patterns of the ligand field absorption bands of the cis and the trans isomers of the halogenocyanobis(ethylenediamine)cobalt(III) ion have been discussed in relation to the geometrical configurations of the complexes and to the σ- and π-antibonding contribution of the cyanide or the halide ligands to the metal d-orbitals. These studies have been made successfully using the circular dichroism data of the optically active cis-[CoX(CN)en2]X (X=Cl, Br).
The X-Ray Structure Determination of Dihydroteleocidin B Monobromoacetate
Authors: Harada Hirokichi , Sakabe Noriyoshi , Hirata Yoshimasa , Tomiie Yujir\={o} , Nitta Isamu
Published: July 2006

The structure of dihydroteleocidin B monobromoacetate, the derivative of a toxic substance teleocidin B produced by some streptomyces, has been determined by X-ray analysis. Crystals of the derivative, C30H44O3N3Br, are orthorhombic (a=14.50, b=26.60, c=7.93Å, z=4, the space group is P212121). The intensities of 2053 reflections were measured using CuKα radiation. The bromine position was determined by Patterson methods, and all the carbon, oxygen and nitrogen atoms were elucidated by three-dimensional minimum function methods. A three-dimensional Fourier synthesis and the least squares methods completed the refinement, giving a final R value of 16.4%. The derivative has a substituted indole nucleus with a nine-membered lactum ring.
The Effects of Polyamines on the Melting of Polyriboadenylic Acid Plus Polyribouridylic Acid Complexes in a Solution
Authors: Higuchi Shigesada , Tsuboi Masamichi
Published: July 2006

Ultraviolet absorptions of aqueous systems of polyriboadenylic acid (poly A) plus polyribouridylic acid (poly U) have been examined with various Na+ and Mg2+ concentrations and at various temperatures. The transition temperatures (Tm) among the two-stranded conformation, poly(A+U), the three-stranded conformation, poly(A+2U), and the two single-stranded conformations, poly A and poly U, were determined. The effects upon the Tm of adding NH3+-(CH2)nNH3+-type diamines (n=2, 3, 4, 5, 6, and 8), spermine, and actinomycin D to the solutions were observed. It was found that these amines stabilize three-stranded poly(A+2U) more than they stabilize the two-stranded (poly(A+U)) and the single-stranded (poly A and poly U) conformations. Among the diamines examined, those with n=2 and 3 values show a greater effect than those with n=4, 5, 6, and 8 values.
Analytical Studies Using the Convection Electrode. XI. Cathodic Stripping Voltammetry of Chloride Ions with the Pushed-out Mercury Drop Convection Electrode
Authors: Suzuki Junsuke
Published: July 2006

The cathodic stripping voltammetry of chloride ions in a potassium nitrate or a nitric acid solution was studied by using the Pushed-out Mercury Drop Convection Electrode (PMDCE) (J. Suzuki and T. Ozaki, This Bulletin, 37, 230 (1964)). The cathodic stripping peak current, ip, depended upon the rotating rate of the disk, ω (600—1000 r. p. m.); the rate of voltage scan, v(100—300 mV./min.); the pre-electrolysis time, t (∼3 min.), and the bulk concentration of chloride ions, C. It was concluded that the corresponding cathodic peak current, ip can be given by the equation:

ip=kvω1⁄2Ct2⁄3

where k is the constant. In a 0.1 m nitric acid solution, it was possible to determine the chloride ions in so dilute a solution as 3×105−  m with a good reproducibility.
Solvent and Steric Effects on the Solvolysis of Polyvinylsulfonic Acid Esters
Authors: Yoshikawa Sadao , Kim Oh-Kil , Hori Takeshi
Published: July 2006

The solvolysis of ethanesulfonic acid esters followed closely first-order kinetics, while the case of polyvinylsulfonic acid esters gave strongly-curved first-order plots according to the solvent composition. With a high acetone content, the solvolysis rates of polymeric sulfonic esters decreased gradually with the lapse of time, while in a high water content, the solvolysis was suppressed at the beginning of the reaction but was accelerated remarkably with the reaction time. The former finding indicates the release from the steric congestion which contributed to the initial rate enhancement, while the latter indicates the aggregation of the polymer molecules owing to their strong hydrophobic character. The solvolysis rates, kp, for polymeric sulfonic esters were much greater than those, km, for monomeric analogs in all cases except isopropyl and n-butyl esters in 20% aqueous acetone. The relative rate (kp/km) increased with an increase in the acetone content and was apparently greater with the methyl ester than with the other esters, and the value of (kp/km) in relation to the methyl ester in 80% acetone content reached 15. Furthermore, it was found that the proton catalysis by the neighboring sulfonic acid formed on the lapse of reaction time was absent, and also that the salt effect was negligibly small.
The Reactions of N,N-Dimethylbenzamide Diethylmercaptole
Authors: Mukaiyama Teruaki , Yamaguchi Tatsuaki
Published: July 2006

The reactions of N,N-dimethylbenzamide diethylmercaptole with active methylene compounds, amines, hydrazines, benzaldoxime, benzhydroxamic acid and heavy metal salts have been studied. Active methylene compounds, hydroxylamine, hydrazine and phenylhydrazine were found to react with N,N-dimethylbenzamide diethylmercaptole to give the corresponding α-dimethylaminobenzylidene derivatives by eliminating ethyl mercaptan. In addition, such heterocyclic compounds as 2-phenylimidazoline, 2-phenyloxazoline and 2,5-diphenyl-1,3,4-oxadiazole were derived from- N,N-dimethylbenzamide diethylmercaptole by cyclization reactions with ethylenediamine, 2-aminoethanol and benzoylhydrazine respectively. Further, it was found that N,N-dimethylbenzamide diethylmercaptole reacted with benzaldoxime and benzhydroxamic acid to give the dehydrated products benzonitrile and phenyl isocyanate respectively. Finally, it was established that heavy metal salts, such as mercuric oxide, mercuric cyanide and silver cyanide, reacted with N,N-dimethylbenzamide diethylmercaptole to liberate heavy metal mercaptides, thus giving N,N-dimethylbenzamide, N,N-dimethylbenzamide dicyanide and N,N-dimethylbenzamide ethylmercaptocyanide respectively.
Studies on d-Glucosamine Derivatives. XIII. The Synthesis of N-Acetyl-1-O-aminoacyl-d-glucosamines
Authors: Yoshimura Juji , Funabashi Masuo
Published: July 2006

For the purpose of examining the properties of the glycosidic ester linkage of sugars to amino acids, N-acetyl-1-O-aminoacyl-d-glucosamines were synthesized. N-Acetyl-4,6-O-benzylidene-d-glucosamine was condensed with an equimolar amount of N-benzyloxycarbonyl amino acids by the dicyclohexylcarbodiimide method, followed by the hydrolytic and hydrogenolytic removal of the protecting groups. N-Acetyl-3-O-acetyl-d-glucosamine was also newly prepared as a contrast compound.
Organoboron Compounds. XI. The Polymerization of Vinylboronic Acid
Authors: Kato Seiji , Kimura Keiko , Nagata Katsuhisa , Tsuzuki Yojiro
Published: July 2006

It has been found that potassium persulfate is a good initiator for the polymerization of vinylboronic acid. With this initiator the polymerization has been studied in acidic as well as in basic medium, and the best conditions for the polymerization have been established with the help of molecular weight determination of the products. The highest molecular weight has been observed in basic medium to be about 7000. A mixed solvent (1:1) of ether and acetone has been used as the precipitant. The variation in the rate of polymerization and the boron content has been investigated in a narrow range of pH, from 6 to 8.
The Dimerization of Ethylene Using Palladous Chloride as the Catalyst
Authors: Kusunoki Yasuo , Katsuno Ryokei , Hasegawa Noboru , Kurematsu Susumu , Nagao Yoshio , Ishii Kanzi , Tsutsumi Shigeru
Published: July 2006

The dimerization of ethylene was carried out using palladous chloride as the catalyst. Acetic acid, ethylene dichloride, ethylene tetrachloride, benzene, chlorobenzene, triethyleneglycol, acetic acid esters, chloroform, cyclohexane and ethanol were employed as the reaction solvents, and the effects of these solvents on the reaction were investigated. The best yield of butylene (about 1500 mol.% to palladous chloride) was obtained, when acetic acid was used as the solvent; the yield decreased gradually following the above order of solvents until, when ethanol was used as the solvent, it yielded only 96 mol.%. However, in all solvents dimerization was carried out predominantly, and only a few higher polymers were obtained. It is very interesting that the solvent effect mentioned above was different from the effect of solvents in the isomerization of olefin when metal carbonyl was used as the catalyst. To explain these results, a hydride ion-shift mechanism has been proposed.
A New Method of Quantitative Differential Thermal Analysis
Authors: Ozawa Takeo
Published: July 2006

This paper presents a rigorous new theory of differential thermal analysis, taking account of the temperature gradient in the sample. From this consideration, a new quantitative method is proposed, where a solid-cell holder of low thermal conductivity is set between a sample cell and a metal block, and a thermocouple is inserted tightly between the outside wall of the cell and the cell holder. By means of this arrangement, the peak area becomes proportional to the heat of transformation, irrespective of the kinds and the states of samples and operational variables. The experimental verification using various samples and the effect of several operational variables, such as the heating rate, the concentration of a diluent, the packing density, and the depth of the packing sample, are also shown; satisfactory results are obtained. Two new concepts, the sensitivity and the response time of the system, are proposed and evaluated. Conventional methods are criticized, and the inherent limitations of differential thermal analysis are discussed.
Proton Magnetic Resonance Spectra of Cobalt(III) Hexammine-type Polyamine Complexes
Authors: Yoneda Hayami , Morimoto Yukiyoshi
Published: July 2006

The proton magnetic resonance spectra of [Co en3]Cl3, [Co tn3]Cl3, [Co pn2]Cl3 and [Co den2]Cl3(den=diethylenetriamine) dissolved in trifluoroacetic acid were measured. All of the observed spectra consist of broad bands, which were assigned on the basis of intensity considerations and by comparing them with the spectra of the corresponding deuterated species. In case of the ethylene-diamine complex, the double-resonance method was applied, measurements at different temperatures were made, and the origin of the breadth of the bands was discussed. The NH2 signals of the ethylenediamine and trimethylenediamine complexes show AB-type features. This was confirmed by comparing the spectra obtained at 60 Mc. and at 100 Mc. The AB-type features of the NH2 signal were explained in terms of the crystal structure of the complex.
Infrared Spectroscopic Study on Ion Association of Hexacyanoferrate(III) and Hexacyanoferrate(II) Ions
Authors: Tanaka Nobuyuki , Kobayashi Yumiko , Kamada Minoru
Published: July 2006

The ion association of hexacyanoferrate(III) and hexacyanoferrate(II) anions with univalent or bivalent cations in aqueous solutions has been studied by the measurement of the infrared absorption band due to the C≡N stretching vibrations. All the solutions measured in which ion-pairs with hexacyanoferrates(III) predominated gave an absorption maximum at 2121 cm−1, and those in which ion-pairs with hexacyanoferrates(II) predominated, at 2020 cm−1, although hexacyanoferrates(III) and hexacyanoferrates(II) of potassium and alkaline earth metals gave different spectra from each other in solid state. No difference in absorption band obtained with different solutions was supported by the distance between two ions in ion-pair, which was estimated from the structures of hexacyanoferrate(III) and hexacyanoferrate(II) ions and the closest approach of the ion-pair; this indicates that there is no direct interaction between the complex anion and the cation, but one or more water molecules interpose between the two ions.
A Spectrophotometric Study of the Complex Formation between Iron(III) and Salicylic Acid
Authors: Ogawa Kin’ya , Tobe Nobuko
Published: July 2006

A spectrophotometric study of the complex formation between iron(III) and salicylic acid was carried out over the pH range up to 6; further, an attempt was made to test the applicability of salicylic acid as a reagent for the spectrophotometric determination of iron (III) in the presence of iron(II). The absorption maxima of the mixture of iron(III) and salicylic acid are found at 530 mμ independently of the pH between 0.7 to 2.5, while they shift to shorter wavelength when the pH rises above 3. The isosbestic point occurs at 550 mμ between pH values from 3 to 6. It was concluded that three complex species, Fe(Sa)+, Fe(Sa)2−, and Fe(Sa)3−3, are formed successively in acid solutions; their stability constants were determined to be:

(Remark: Graphics omitted.)

where Sa2− denotes the salicylate anion, C6H4(O−)(COO−). If the pH of the solution is adjusted from 2 to 3 and if absorbancy measurements are made at 515 to 500 mμ, salicylic acid can be used as a reagent for determining iron(III) in the presence of iron(II). The optimum concentration of iron(III) is 2 to 12 p. p. m.; iron(II) does not interfere, even at a concentration of 100 p. p. m.
The Lifetime of Excimer Fluorescence of Naphthalene
Authors: Azumi Tohru , Azumi Hiroshi
Published: July 2006

The radiative lifetimes of the excimer fluorescence of naphthalene are calculated for excimers of various geometrical configurations. The results vary, to a great extent, with the configurations, but with a previously-suggested configuration the calculated lifetime is 6×10−6 sec. This is within a factor of 5 of the experimental results.
Intermediates in the Photoreduction of Eosine as Revealed by a Flash-Photolysis Study
Authors: Ohno Takeshi , Kato Shunji , Koizumi Masao
Published: July 2006

Besides the triplet state, semi-reduced eosine (Rd) and semi-oxidized eosine (Ox) were observed as transient intermediates in an aqueous solution; the former has a peak at 408 mμ, and the latter, one at 456 mμ. These two species are produced by the reaction DT+D→Rd+Ox or DT+DT→Rd+Ox. The sum of the rate constants for the reactions DT+D→Ox-+Rd and DT+D→2D is about 8.0×108  m−1 sec−1, approximately equal to the sum of the rate constants for DT+DT→2D and DT+DT→Ox+Rd. Triplet eosine, by reacting with ATU or EDTA, produces two kinds of half-reduced eosine, Rd′ and Rd″, which have absorption spectra similar to those of Rd but with different life-times. These are perhaps loose compounds of half-reduced dye and a half-oxidized reductant. The rate constants for DT+ATU→Rd′ and DT+EDTA→Rd″ are 3.4×105  m−1 sec−1 and 5×105  m−1 sec−1 respectively. Rd disappears bimolecularly by means of the Rd+Ox→2D reaction with the rate constant of 8.8×107  m−1 sec−1. Ox, by reacting with EDTA or ATU, regenerates the original dye with the rate constants of 1×106 and 8×105  m−1 sec−1 respectively. The results enable us to conclude that the D–D mechanism occurs under suitable conditions.
The Electronic Spectra of 1,1′-Dianthrylpoly-ynes
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi , Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

The electronic spectra of 1,1′-dianthrylpoly-ynes have been studied by Hückel MO theory on the basis on various approximations for resonance integrals. A good agreement between theoretical and experimental values is obtained from a modified bond-alternation approximation. This result shows that the contribution of a cumulene-type ionic structure to the ground state of the molecule increases with an increase in the number of the triple bonds.
Studies of the Aqueous Solution of a Surface Active Substance by Means of an Ultrasonic Interferometer. II. The Effects of Added Electrolytes on the Dissolved State of Sodium Alkyl Sulfate
Authors: Shigehara Koji
Published: July 2006

The sound velocity (U) and the density of aqueous solutions of sodium dodecyl (SDS) and octyl (SOS) sulfates with inorganic electrolyte have been measured by using a differential ultrasonic interferometer and a float balance respectively, and the compressibility (β) has then been calculated from these results. The CMC’s of SDS solutions of various concentrations of sodium salts have been determined from U-vs.-SDS and β-vs.-SDS concentration (C2) diagrams. The results show a linear relationship between the logarithm of CMC and the logarithm of the concentration of sodium ions. The values of dβ⁄dC2 below CMC are affected by the addition of electrolytes, while the values above CMC are almost not affected at all by the addition of electrolytes. The diagrams of dβ⁄dC2 of alkyl sulfate vs. the number of carbon atoms in alkyl sulfate molecules with varying concentrations of added electrolytes showed straight lines which all passed through the same point when extrapolated to a zero number of carbon atoms. These results have been explained by taking account of the dissolved state of a surface active substance under the builder action of added inorganic electrolytes, which action decreases not only the mutual repulsion of the ionized-head group of a surface active substance but also the non-ionic hydration of the CH2-chain of the surface active substance.
The Reactions of t-C4H9+ in the Radiolysis of Neopentane in the Gas Phase
Authors: Miyazaki Tetsuo , Shida Shoji
Published: July 2006

The yields and reactions of t-C4H9+ produced in the radiolysis of neopentane in the gas phase have been studied by the use of ammonia. The yields of iso-C4H8 increase sharply upon the addition of a small amount of ammonia in the radiolysis of neopentane and show a constant value upon the further addition of ammonia (more than 10 mol.%). Since this increase is due to the following reaction:

t−C4H9++NH3→ iso−C4H8+NH4+

we get G(t-C4H9+)=1.76 by assuming the increment of iso-C4H8 to be equal to the yield of t-C4H9+. This value is consistent with the value expected from the mass spectrum of neopentane. It has, therefore, been concluded that the ammonia method is a very effective general method for studying the reactions of ions. It is applicable to the study of ions under high pressures, ions which can not be studied by a mass spectrometer. It is especially effective in the study of less reactive ions.
The Superstructure in Fine Aragonite Particles
Authors: Hiragi Yuzuru , Kachi Sukeji , Takada Toshio , Nakanishi Norihiko
Published: July 2006

An electron diffraction study was done with fine aragonite particles about 0.5 to 1.0 μ in size. The specimens were obtained by mixing a boiled calcium chloride solution (0.1 n) with 0.1 n of an ammonium carbonate solution. Extra spots were observed with half-integer indices {1⁄2,1⁄2,l}. This suggests the existence of a structure that differs from that of normal aragonite. From an X-ray diffraction study of the specimen, a {1/2, 3/2, 0} diffraction was also observed. The structure for explaining these half-integer diffractions is presented as a superstructure of aragonite; it belongs to the space group of D2h15−Pbca, with cell dimensions of A=8.420 Å, B=9.385 Å, and C=5.741 Å, and it containes 8 formula units in a unit cell. A dark-image photograph shows this anomalous area to be comparatively wide and suggests that the anomalous area is dominant in a crystal. The authors conclude that rapidly-precipitated aragonite powders contain a small quantity of the repeatedly-twinned crystals mentioned above.
Non-Debye Reorientation Processes of Molecules. Correlation Functions and Spectral Densities for Spherical Molecules
Authors: Shimizu Hiroshi
Published: July 2006

The non-Debye reorientation processes in which the Debye equation is inapplicable are studied for spherical molecules by using an equation proposed by the author. The physical meaning of the angular correlation in the non-Debye processes is discussed in detail. It is shown that in the non-Debye processes the non-dissipative decay of the mutual-phase correlation of rotating molecules must be taken into account, in addition to the dissipative decay due to molecular collisions, and that the use of the “microscopic viscosity” in the Debye equation is not plausible. It is also shown that, in contrast to the Debye processes, there is no one-to-one correspondence between the correlation time for molecular reorienation and the mean life time of the rotation, since the contribution from the nondissipative decay should be considered also. The vector and the tensor correlation functions,

〈cosθ(0)cosθ(t)〉 and 〈(1⁄2){3cos2θ(0)−1}{(1⁄2)3cos2θ(t)−1}〉,

and the corresponding spectral densities, the band shapes of infrared and Raman spectra respectively, are obtained theoretically for various conditions and are shown graphically. As illustravtie examples of the treatment, methane and deutero methane molecules are studied. Vector correlation functions are obtained from the observed band shapes of the infrared spectra of these molecules. Comparing the theoretical correlation functions with experimental ones, it is shown that a reasonable agreement between theory and experiment is obtained and that methane molecules have a typical non-Debye reorientation process even below the freezing point. Some characteristic features of the non-Debye process are also discussed.
A Study of the Hydration of Calcium Orthoplumbate. VII. The Mechanism of the Formation of Hydrate
Authors: Koishi Masumi
Published: July 2006

The hydration processes of calcium orthoplumbate are studied by means of a twin-type conduction calorimeter. The curves of the differential electromotive force vs. the hydration time have two characteristic maxima, corresponding to two exothermic processes: the first one is due to the immersion and dissolution of calcium orthoplumbate, while the second one is caused by the formation of crystalline hydrates. The heat liberated by the first process is about 1.14 cal./g. Ca2PbO4, while that liberated by the second process is about 52.22 cal./g. Ca2PbO4. The reaction in the second process proceeds by the 2/3 order; this may be explained by assuming that the rate of the reaction is determined by the surface area of the calcium orthoplumbate being hydrated.
Metal Complexes of Amino Acids. III. The Circular Dichroism of Cobalt(III) Ammine and Ethylenediamine Complexes with l-Amino Acids
Authors: Yasui Takaji , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

In order to study the vicinal effect of the l-amino acid coordinated in a complex on the central metal ion, a number of cobalt(III) l-amino acid complexes of three types were prepared, i. e., [Co(NH3)5(l-amH)]X3, [Co(l-am)(NH3)4]SO4, and trans-[Co en2(l-amH)2]X3, where l-amH denotes an l-amino acid, and where X is Cl, Br, or I. The circular dichroism (CD) and the rotatory dispersion (RD) spectra of their aqueous solutions were measured in the wavelength range from 650 to 300 mμ. In the region of the first absorption band, both the [Co(NH3)5(l-amH)]3+ and the trans-[Co en2(l-amH)2]3+ ions show one or two CD bands to be expected in complexes of the C4v symmetry with a structure of the [Co N5O]-type and of the D4h symmetry with a structure of the trans-[Co N4O2]-type respectively. The positions of the CD bands observed in the trans complexes coincide well with the maxima of the split components, Ia and Ib, of the first absorption band. The CD spectra of different [Co(l-am)(NH3)4]2+ ions, in which l-am is a bidentate ligand, show a variety of behavior; they are discussed from a stereochemical point of view. An intense CD band of the [Co(l-prol)(NH3)4]2+ ion at about 510 mμ can be attributed to the vicinal effect of an asymmetric nitrogen atom of the coordinated l-prolinate ion. For the trans-[Co en2(l-amH)2]X3 complexes, the rotatory parameters and rotatory strengths were calculated by means of analyses of the experimental CD and RD curves.
Studies of the Organic Reaction of Metal Carbonyl. X. The Oxo Reaction of Ethyl Acrylate—The Effects of the Reaction Conditions on the Distribution of the Products
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa
Published: July 2006

The ratio between the α- and β-carbethoxypropionaldehyde formed in the oxo reaction of ethyl acrylate is affected by various reaction conditions; the proportion of β-carbethoxypropionaldehyde increases with an increase in the reaction temperature, but decreases with an increase in the partial pressure of carbon monoxide or hydrogen. These effects can be explained on the basis of the reaction mechanism between cobalt hydrocarbonyl and ethyl acrylate (Y. Takegami et al., This Bulletin, 37, 1190 (1964)): in the first step of the reaction, ethyl acrylate reacts with cobalt hydrocarbonyl to give, selectively, α-carbethoxypropionylcobalt carbonyl (I), and then I isomerizes to β-carbethoxypropionylcobalt carbonyl (II). Accordingly, the rates of two competitive reactions, the isomerization of I to II and the reduction of I to the corresponding aldehyde, may be the factors determining the distribution of the oxo reaction products. Under the oxo reaction conditions, the isomerization of I to II seems to occur more easily at a relatively high temperature and to be prohibited by a high pressure of carbon monoxide. On the other hand, a relatively high pressure of hydrogen seems to be favorable to the reduction of I to the aldehyde.
Studies of Acenaphthene Derivatives. XII. On the Red Substance Obtained from Acenaphthenequinone and Ammonia
Authors: Tsuge Otohiko , Tashiro Masashi
Published: July 2006

In order to elucidate the chemical structure of red crystals (A) obtained from the reaction of acenaphthenequinone (I) with ammonia, the reaction of I with ammonia, formamide or benzylamine was reinvestigated. It has been made clear again that the compound A is not acenaphthazine (II) but acenaphtho[l, 2-b]isoimidazole-2-spiro-2′-acenaphthenone (III), and that Schonberg’s assumption of the structure of the compound A is incorrect. That reaction of I with benzylamine afforded II as yellow needles in a good yield. Also, it has been found that the reaction product (B) of I with formamide is a mixture of almost equal amounts of II and III.
The Crystal Structure of m-Hydroxybenzamide
Authors: Katsube Yukiteru , Sasada Yoshio , Kakudo Masao
Published: July 2006

Crystals of m-hydroxybenzamide are monoclinic with four molecules in a unit cell of dimensions a=11.59, b=5.03, c=15.53 Å, β=136.1°, space group P21⁄c. An approximate angular orientation of the molecule in the cell was quickly obtained by an application of the vector-set seeking method. The location of the molecule was then determined with the help of the orientation. The positional and anisotropic thermal parameters of the carbon, nitrogen and oxygen atoms were refined by means of the least-squares method with three-dimensional intensity data. The final R factor was 0.138. The carboxyamide group and benzene ring twist to each other about the C-C bond by an angle of 24.4°. The interatomic distances and bond angles are close to those expected. The molecules are linked by three types of hydrogen bonds to form the infinite double-layered sheets perpendicular to the c axis, and the crystal structure shows somewhat different features from those of the related compounds.
The Quenching Action of Benzoic Acid and Methylbenzoate on the Fluorescence of Naphthalene Derivatives. III. The Solvent Effect on the Quenching of the Fluorescence of Dimethylnaphthylamine by Methylbenzoate
Authors: Miwa Takuji , Koizumi Masao
Published: July 2006

The fluorescence and absorption spectra and the quenching of the fluorescence of N, N-dimethyl-2-naphthylamine by methylbenzoate have been measured in cyclohexane, benzene, p-dioxane, isopropyl ether, ethyl ether, ethyl acetate, tetrahydrofuran, acetone and N, N-di-methylformamide (in the order of DK values). The fluorescence and the absorption spectra show a red-shift with the polarity of the solvent. By the method of Lippert and Mataga, the dipole moment of the excited fluorescer molecule has been estimated to be 4. ID. In nonpolar and weakly polar solvents, the methyl benzoate-added systems give fluorescence spectra with a swell or a shoulder on the long wavelength side, but this does not occur in N, N-dimethylformamide. When methyl benzoate is used as the solvent, two peaks of fluorescence are observed. The new emission has been interpreted as a charge-transfer emission, and the temperature-dependence of the fluorescence spectra has led to the conclusion that an encounter of fluorescent and quencher molecules is prerequisite for the appearance of CT emission. The quenching efficiencies in different solvents have been dealt with in reference to that in N, N-dimethylformamide, since the quenching in this solvent has been found to be almost encounter-controlled. A general correlation has been found between the quenching efficiency and the polarity of the solvent. The quenching mechanism and also the appearance of the CT emission have been discussed.
Studies of the Chemiluminescence of Several Xanthene Dyes. III. The Effect of Added Foreign Dyes on Light Production
Authors: Kamiya Isao , Iwaki Ryojirô
Published: July 2006

The intensity of uranine chemiluminescence decreased when trypaflavine was added to the system. The enfeebling action seemed to be due to external quenching. On the contrary, the intensity of eosine chemiluminescence was enhanced by the presense of uranine. The values of Δ and σ are defined by the following equations:

(Remark: Graphics omitted.)

where IUE, IU and IE are the intensities measured in uranine-eosine, uranine and eosine systems respectively, and where T is the duration of eosine chemiluminescence. Δ increased with the increase in either the concentration of uranine or that of eosine, while σ increased only when the ratio of the uranine concentration to the eosine concentration increased. Δ increased with the increase in the temperature, while σ was little affected by the temperature. Δ increased upon the addition of organic solvents, while σ was little affected by the addition of the organic solvents. The enhancing action is due neither to the production of a stable compound which emits strongly nor to the increase in the rate of the decomposition of the dye. One possible mechanism of the enhancing action is that energy is transferred from an energy-rich intermediate produced by the reaction to an unoxidized uranine or eosine.
Studies of Poly-β-benzyl-l-aspartate Helix. II. The Circular Dichroism and Optical Rotatory Dispersion of Copolymers of β-p-Methyl, Chloro, or Cyanobenzyl-l-aspartate with β-Benzyl-l-aspartate
Authors: Hashimoto Masahisa
Published: July 2006

The observation of the circular dichroism (240–290 mμ) due to the aromatic side chain indicates that, in a chloroform solution, even the side-chain aromatic rings of the copolyaspartate chain in the right-handed helix are in a regular arrangement to form an outer helix. On the contrary, for the copolyaspartate chain in the left-handed helix, the aromatic rings are much less regular. The ORD measurements indicate that, in a dimethylformamide solution, the poly-β-benzyl-l-aspartate chain is essentially in a random coil form, whereas the para-substituted derivatives are essentially in a right-handed helix. Accordingly, for each series of copolymers, the transition from a random coil form to a right-handed helix is observed as the molar content of the para-substituent is increased. The copolypeptide chain of β-benzyl-l-aspartate and β(p-methylbenzyl)-l-aspartate (molar ratio, 1:1) takes either the left-handed helix in a chloroform solution or the right-handed helix in a dimethylformamide solution. Accordingly, for this copolypeptide, the transition from the left to right-handed conformation is observed at the mixing volume ratio, 90 : 10, of the chloroform-dimethylformamide solution.
Syntheses of l-Sorbosylthymines and Related Compounds
Authors: Tokuyama Kanji , Katsuhara Mitsuru
Published: July 2006

1, 3, 4, 5-Tetra-O-acetylsorbopyranosylureas were prepared from sorbopyranosyl chloride via 1, 3, 4, 5-tetra-O-acetylsorbopyranosylisocyanates. 1-Ureido- and 6-ureidosorbofuranoses were obtained from the corresponding aminosorboses. The transformations of the ureas thus obtained into N-(sorbose)thymines were achieved, although with difficulty, by the direct condensation of halogeno- or tosylsorboses with metal salts of thymine.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. III. The Effect of the Monomer Concentration
Authors: Higashimura Toshinobu , Miki Tetsuro , Okamura Seizo
Published: July 2006

In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the monomer concentration on the polymerization reaction has been studied. The kinetic order of the monomer concentration as determined from the course of polymerization is close to 2 (except in a non-polar solvent). The kinetic order of the initial monomer concentration is extraordinarily large in the polar solvent. On the other hand, the molecular weight of the polymers formed increases with an increase in the initial monomer concentration. In the polymerization of trioxane in a polar solvent such as nitrobenzene at a low monomer concentration, the molecular weight of the polymers does not increase in the course of polymerization, even at the initial stage of polymerization. The reason for this has been discussed in terms of the nature of the chain carrier.
The Hydroxide-Blacks of Ruthenium and Rhodium as Catalysts for the Hydrogenation of Organic Compounds. II. The Effects of Solvents and Added Alkalis in the Hydrogenation of Aniline
Authors: Nishimura Shigeo , Shu Tetsuo , Hara Tomoyoshi , Takagi Yuzuru
Published: July 2006

The hydrogenation of aniline with the hydroxide-black catalysts of ruthenium and rhodium was investigated, using various alcohols as solvents. The formation of dicyclohexylamine increased in the following order with respect to the solvents: t-butyl alcohol≅isopropyl alcohol << ethyl alcohol < methyl alcohol. It was shown that the addition of a small amount of alkali greatly hinders the formation of dicyclohexylamine. The effects of added ammonia and dicyclohexylamine were also investigated. The addition of ammonia retarded the rhodium-catalyzed hydrogenation much more seriously than the hydrogenation with ruthenium, but it was found that in the presence of alkali the hydrogenation with rhodium was not inhibited by the addition of ammonia.
An Analysis of the Proton Magnetic Resonance Spectra of Acrylic Acid in Solution: A Comparative Discussion of the Methods of the Analysis of ABC Spin Systems
Authors: Yamamoto Takeo , Fujiwara Shizuo
Published: July 2006

In an attempt to examine various existing methods for the analysis of high-resolution NMR spectra, the statistical theory has been applied to the least-squares iteration method presented by Arata, Shimizu and Fujiwara. The standard errors of chemical shifts and spin-spin coupling constants, and the singularity in the normal equation, have been discussed. Two sets of parameters which are placed close together have a possibility of producing a singularity in the normal equation. A way of eliminating the singularity has been presented. The method thus presented has then been applied to an analysis of the vinyl proton spectra of acrylic acid in carbon tetrachloride and in aqueous solutions of various pH values. It has been found that the spin-spin coupling constants do not change beyond the range of experimental errors under the conditions of the present study. The change in chemical shifts has been discussed in terms of the possible conformations of the molecules.