bluuebunny/crossref_metadata_2025 huggingface dataset:
An NMR Study of Metal Complexes Containing Acetylacetone and Related Compounds. I. The Preparation, Halogenation and NMR Spectra of Cobalt(III) Complexes Containing Acetylacetone and Bis(acetylacetone)ethylenediimine
Authors: Fujii Yuki
Published: July 2006

A mixed cobalt(III) complex containing both bis(acetylacetone) ethylenediimine and acetylacetone anions, [Co(bean)(acac)] (bean=dianion of bis (acetylacetone) ethylenediimine, acac=anion of acetylacetone), was newly prepared and its electrophilic substitution reaction at the chelate ring protone was studied by means of NCS, NBS, and NIS (NCS, NBS and NIS are the abbreviated forms of N-chloro-, N-bromo- and N-iodosuccinimide). The structures of this complex, [Co(baen)-(acac)], and of the halogenated complex were both determined to be of the β-form (cis with respect to the coordinated two oxygen atoms of baen) on the basis of their NMR spectra. The ring protons of the imine chelates were found to be more reactive than that of the acetylacetone chelate in the chlorination reaction. Then, a bi-substituted complex, [Co(baen-Cl2)(acac)], in which two chlorine atonies were attached to the two imine chelate rings, was prepared. Tri-substituted complexes, [Co(baen-X2)(acac-X)] (X=Cl, Br and I), were also prepared. The quasiaromaticity of both the acetylacetone and imine rings was considered on the basis of their NMR spectra. A new complex, [Co(baen)(OH)(H2O)], was also prepared in order to assign the NMR spectrum of the complex, [Co(baen)(acac)]. The IR, UV, and visible absorption spectra were also considered.
The Transformation of the Triphenylmethyl Radical into the Triphenylmethyl Cation in the Sulfur Dioxide - Oxygen System
Authors: Takeuchi Hiroshi , Nagai Toshikazu , Tokura Niichiro
Published: July 2006

The decomposition of phenylazotriphenylmethane (I) in the presence of SO2 and O2 in benzene at 60°C gives p-hydroxytetraphenylmethane (II) by the reaction of the trityl cation and the phenol formed in the reaction system. However, in the absence of O2 or SO2, the above-mentioned reaction produces trityl phenyl sulfone (III) or bistrityl peroxide (IV), without forming any II. Also, 1-diphenylmethylene-4-trityl-2,5-cyclohexadiene (Gomberg’s trityl) (V) has been chosen as the trityl radical source, and reacted with phenol in the presence of SO2 and O2 to give II as the product. However, in the absence of SO2, IV and a trace of II are formed. Moreover, in the absence of O2 in the above system, p-benzhydryltetraphenylmethane (VI) and a small amount of II are formed. The benzene solution of VI is stable on exposure to air at 60°C. Further, the UV spectrum of V in the liquid SO2-O2 system shows λmax at 405 mμ (logε 4.1) and 434 mμ (logε 4.1) (trityl chloride in 98% H2SO4: λmax 430 mμ (logε 4.58)). However, the UV spectrum of VI in the liquid SO2-O2 system has no absorption in this range. The NMR spectrum in the liquid SO2-O2 system of V exhibits only aromatic protons (2.6–3.1 τ). These facts indicate that the trityl radical generated from V is transformed into the trityl cation in the SO2-O2 system at room temperature, whereas VI does not dissociate into the trityl radical even at 60°C in benzene.
Relations between Intramolecular Energy Transfer Efficiencies and Triplet State Energies in Rare Earth β-diketone Chelates
Authors: Sato Susumu , Wada Masanobu
Published: July 2006

The fluorescence yield of europium chelates in several solutions varies, through its maximum value, with the increase in the energy difference between the triplet state of a ligand and the emitting level of an europium ion. The time-resolved spectroscopic measurements show that the excitation energy is transferred from the triplet state to the lower and nearest resonance level of the europium ion. The intramolecular energy transfer mechanisms for europium chelates and terbium chelates are proposed, taking the resonance exchange interaction and the thermal deactivation processes from the emitting levels of rare earth ions into consideration. Steady-state rate equations are made, and the equation of the fluorescence yield is obtained. Thus, the relations between the fluorescence yield and the triplet state energy are estimated and the fluorescence properties of rare earth β-diketone chelates may be qualitatively described.
Effects of Iodine Addition on the Electrical and Optical Properties of the Semiquinoid Phenothiazine Bromide
Authors: Matsunaga Yoshio , Shono Kosuke
Published: July 2006

The electrical resistivity and the electronic and vibrational spectra of the semiquinoid phenothiazine bromide have been found to be drastically modified by the addition of iodine. The resistivity minimum lies around the mole ratios of 0.25 to 0.30, while the value in this composition range is from 4 to 5 ohm cm. The combined spectroscopic data indicate three different stages in the intermolecular interactions in this system; the first around a mole ratio of 0.25, the second near 0.5, and the third above 1.00. The higher the iodine content, the less conductive the adducts appear to be. Iodine addition was attempted also to the p-phenylenediamine bromide; however, no pronounced effect on the physical properties could be found in this system.
Polarography of Halides in Dimethylformamide. III. The Chloride Ion, the Trichloromercurate Ion, and Mercuric Chloride
Authors: Matsui Yoshihisa , Kurosaki Yukio , Date Yoshio
Published: July 2006

The polarographic behavior of the chloride ion at the dropping mercury electrode was investigated in dimethylformamide. The chloride ion gives two diffusion-controlled anodic waves. On the basis of the analysis of the waves, the first anodic wave can be ascribed to the reversible oxidation of mercury to form either the tri- or the tetrachloromercurate ion. At the more negative part of the potential in the wave, where the concentration of the chloride ion on the mercury drop is much higher than that of the mercuric ion dissolved, the higher complex species, i.e., the tetrachloromercurate ion, is the main product of the electrode reaction. As the potential of the dropping electrode shifts toward less negative potentials, the concentration of the chloride ion at the electrode surface decreases more and more and the formation of the trichloromercurate ion becomes predominant. When a constant diffusion current is attained, only the trichloromercurate ion is formed and the formation of the tetrachloromercurate ion can be neglected. On the other hand, the second anodic wave can be ascribed to the reversible oxidation of mercury to mercuric chloride.
Mössbauer Effect of 119Sn in Some Organotin Compounds
Authors: Wynter Clive , Chandler Louis
Published: July 2006

Mossbauer, NMR, and infrared spectroscopy have been applied to the study of a number of organometallic tin compounds containing one or more tin manganese pentacarbonyl bonds. For the (CH3)4−nSn[Mn(CO)5]n series (n=0 to 3) a linear relation between the Mössbauer isomer shift and the number of manganese pentacarbonyl ligand was consistent with the partial isomer shift theory of 119Sn. A linear relation between the Mössbauer isomer shift and the methyl proton NMR chemical shift was also observed for this series. A plot of the isomer shift (δ0) versus the number of p holes (hp) for organotin manganese pentacarbonyl compounds established a relation δ0=1.23+0.53hp for sp3 hybridized tin. From isomer shift systematics a value of (ΔR⁄R) for 119Sn was calculated to be 1.2×10−4.
The Synthesis and Polymerization of Vinyl- and Isopropenyl-s-triazines
Authors: Yuki Yasuo , Kakurai Toshio , Noguchi Tatsuya
Published: July 2006

Some new vinyl monomers with an amino-s-triazinyl group were synthesized. 2,4-Amino- and substituted amino-6-vinyl-s-triazines were synthesized by the reaction of the substituted biguanides with acrylyl chloride, while 2-amino-4-substituted amino-6-isopropenyl-s-triazines were prepared from the substituted biguanides with methyl methacrylate. It has been found that vinyl-s-triazines thermally polymerized immediately after melting and gave insoluble polymers. Polymers with amino-s-triazinyl groups in the side chain were obtained by the radical polymerization of some vinyl- and isopropenyl-s-triazines. The copolymerization of these monomers with styrene has been investigated in dimethyl sulfoxide using α,α′-azobisisobutyronitrile as an initiator. The monomer reactivity ratios were determined, and the Q and e values for these vinyl-s-triazines were calculated. Some discussions are presented.
Stereochemistry and Mechanism of Catalytic Hydrogenation and Hydrogenolysis. III. Catalytic Hydrogenolysis of Benzyl-type Alcohols and Their Derivatives
Authors: Mitsui Sekio , Imaizumi Shin , Esashi Yasuyoshi
Published: July 2006

In order to obtain evidence for the mechanism we proposed of the catalytic hydrogenolysis of benzyl-type alcohols and their methyl ethers, optically active 2-phenyl-2-butanol (Ia), 2-phenyl-2-methoxybutane (IIa), ethyl atrolactate (Ib), and ethyl 2-phenyl-2-methoxypropionate (IIb) were hydrogenolyzed over Raney nickel and Pd(H) catalysts under hydrogen or helium atmosphere in an ethanol solution. In all cases, the hydrogenolysis proceeded stereoselectively with retention of configuration over Raney nickel catalyst but with inversion of configuration over palladium catalyst. A reverse stereoselectivity was observed when the benzyl alcohols (Ia and 2-phenyl-1,2-dihydroxypropane (Ic)) and methyl ethers (IIa) and (IIb) were hydrogenolyzed in the presence or absence of various additives over nickel catalysts. It was also found that the hydrogenolysis of benzyl alcohols always proceeds with retention of configuration over nickel catalyst containing sodium hydroxide. Various binary mixtures of Ia, IIa, Ib and IIb were hydrogenolyzed competitively over Raney nickel and Pd(H) catalysts. The order of relative rates was found to be Ia\gtrsimIb\gtrsimIIa\gtrsimIIb over Raney nickel, and IIa\gtrsimIa>>IIb\gtrsimIb over Pd(H) catalyst. The results support our mechanism. The catalytic hydrogenolysis is a competitive reaction of two courses (SNi type and SN2 type reactions), and the stereoselectivity reflects the difference of the free energy levels of the transition states to form π-benzylic complexes. The free energy levels of the corresponding transition states depend on stereoelectronic factor, affinity of substituents for catalyst metal, catalyst hindrance and electronic effects of substituents. The acetates (IVa) and (IVb) of Ia and IIa were hydrogenolyzed with inversion of configuration over nickel and palladium catalysts, whereas the stereoselectivity of the hydrogenolysis of the benzoate (V) of IIa depended on the kind of catalyst. The results are also explained on the basis of our mechanism.
Cationic Arylation. I. Phenylation of Substituted Benzenes with Benzenediazonium Tetrafluoroborate in Homogeneous Solution
Authors: Kobayashi Michio , Minato Hiroshi , Yamada Eiichi , Kobori Nobumasa
Published: July 2006

Substituted benzenes were phenylated with benzenediazonium tetrafluoroborate in homogeneous solutions with DMSO or acetonitrile. The distribution of substituted biphenyls and the partial rate factors indicated that this phenylation was an electrophilic substitution, but the selectivity was much smaller than those of nitration or sulfonylation. Experiments with chlorobenzene-4d, anisole-4d and chlorobenzene-d5 showed that both the orientation and partial rate factors did not change with deuterated compounds. Therefore, it was established that the rate-determining step was the addition of phenyl cation to an aromatic nucleus, and not the abstraction of proton from the phenylated intermediate.
Chemical Constituents of Alnus firma (BETULACEAE). I. Phenyl Propane Derivatives Isolated from Alnus firma
Authors: Asakawa Yoshinori
Published: July 2006

Viscous substances extracted from young shoots of Alnus firma were investigated, and two new hydroxyketones, named yashabushiketol (I) and dihydroyashabushiketol (II), trans-stiihene (III), β-phenylethyl cinnamate (IV), pinostrobin (V), alpinetin (VI), cinnamic acid (VII), paraffin hydrocarbons (n-, anteiso and iso) and triglycerides were identified on the basis of the chemical and spectral data. The biosynthetic pathways of the above aromatic compounds were discussed.
Reaction of Salicylamine with α-Dicarbonyl Compounds. II. Formation of 2,2′-Bibenz-1,3-oxazines
Authors: Kanatomi Hajime , Murase Ichiro
Published: July 2006

The compounds of a new type, 2,2′-bibenz-1,3-oxazine and its derivatives have been synthesized by the reactions of salicylamines with glyoxal or α-diketones in methanol at a temperature lower than 20°C. The oxazine structures were confirmed by infrared spectroscopy in solid state and by NMR spectroscopy in CCl4, CDCl3 and chlorobenzene. An oxazine-Schiff base equilibrium was observed in pyridine and in hot chlorobenzene by NMR spectra. It was found that hydrolytic decomposition of 2,2′-dimethyl-2,2′-bibenzoxazine leads to the formation of salicylidenesalicylamine through transamination. The mechanisms were investigated spectrophotometrically.
Chemical Species Produced from Some Diazaazulene Derivatives in Aqueous Solutions of Various Acidities
Authors: Tanizaki Yoshie , Hiratsuka Hiroshi , Hoshi Toshihiko
Published: July 2006

Making use of the isosbestic points which appear in equilibrium between two chemical species, the chemical structures of various species produced from the diazaazulene derivatives have been investigated in aqueous solutions over a wide pH range. For 1-hydro-1,3-diazaazulene-2-one (abbreviation, HDA-1), for instance, four different species exist as stable species in the respective regions; (a) the pH region higher than 12, (b) around the neutral state, (c) the pH value of ca. 1.5, and (d) the strong acid state. In the (a) region, H+ is taken off from the amino nitrogen of HDA-1 and the species becomes HDA-1−; in (b) the species takes the HDA-1 structure, as its name indicates; in (c) it takes the H+-HDA-1 structure protonated at the aza nitrogen, and in (d) it takes the H+-HDA-1-H+ structure, in which the position of the second protonation could not be clarified. In the case of 2-ethoxy-1,3-diazaazulene (EDA-2), the species corresponding to the second protonation (H+-EDA-2-H+) is hydrolyzed by acid catalysis and becomes H+-HDA-1-H+. In order to interpret the spectra of azaazulene compounds and the spectral change due to protonation, calculations by the LCAO–ASMO–SCF–CI method have been made for 1,3-diazaazulene and EDA-2. The characters of the first and the second transitions of the compounds have been satisfactorily explained by the diagrams of the AO coefficients of the LCAO-MO’s representative of the transitions.
Dielectric Relaxation and Molecular Structure. I. Dielectric Relaxation in Substituted Anilines
Authors: Srivastava K K , Vij J K
Published: July 2006

Measurements of static dielectric constant at 1 Mc, refractive index (for sodium D-line) and complex dielectric constant at 9.44 GHz (X-band) have been made to determine the relaxation times and dipole moments of N,N′-dimethylaniline (A), N,N′-diethylaniline (B), o-chloroaniline (C), m-chloroaniline (D) and p-chloroaniline (E) in dilute solutions of non-polar solvents. Substances A, B, C and D have been studied in n-heptane, benzene decalin and Nujol. The measurements for A and B have also been extended to cyclohexane, whereas E has only been studied in benzene. The values of relaxation time, calculated by Higasi’s equations in terms of a0, a′, a″ and a∞, and those of α, calculated from Cole-Cole’s equation in terms of the same parameters, showed an evidence for the existence of more than one relaxation mechanism. This has been interpreted in terms of the intramolecular rotations of the amino (or the substituted amino) group occurring simultaneously with the overall molecular orientation.
ζ-Potentials of Natural and Synthetic Fibers in SDS Solutions and the Viscosity of SDS Solutions above the Critical Micelle Concentration
Authors: Iwadare Yoshio , Suzawa Toshiro
Published: July 2006

In order to investigate the adsorption behavior of an anionic surfactant on fibers, the ζ-potentials of natural and synthetic fibers in aqueous solutions of sodium dodecyl sulfate (SDS), mainly above the critical micelle concentration (CMC), were measured. Further, the change in the structure of the SDS micelle in aqueous solutions was studied by means of the viscosity method. At first the reduced viscosity for the SDS micelle, ηspm/cm (cm: the micellar concentration), increased rapidly with the cm as long as the cm was small; thereafter, after a break, it approximated the saturated values as a whole. The results calculated from the experimental data using Jones and Dole’s equation showed two distinct breaks. The first break corresponded to the 1st CMC, and the second, nearly to the break in the ηspm/cm  vs.  cm curve. In addition, the intrinsic viscosity for the SDS micelle, [η]M, and the effective specific volume, V, were obtained. From these results, it can be assumed that the structure of the SDS micelle is variable at the break in the ηspm/cm  vs.  cm curve. The ζ-potentials of fibers in aqueous SDS solutions changed rapidly with an increase in the concentration of SDS, but they remained approximately constant in the vicinity of the CMC. At much higher concentrations above the CMC (in the vicinity of the SDS concentration of 2×10−2 mol/l), the ζ values again gradually changed; thereafter, after a break, they became nearly constant again. The change in the ζ-potentials corresponds approximately to the break in the ηspm/cm  vs.  cm curve. Therefore, it may be suggested that it is connected with the change in the structure of the SDS micelle.
Magnetic and Optical Properties of Ionic Electron-Donor-Acceptor Complexes
Authors: Sato Yoichiro , Kinoshita Minoru , Sano Mizuka , Akamatu Hideo
Published: July 2006

The magnetic susceptibilities and optical absorption spectra of a number of ionic electron-donor-acceptor complexes have been studied in a solid state. The complexes of N,N,N′N′-tetra,-methyl-p-phenylenediamine with o-chloranil and o-bromanil were found to have a composition of 2 : 3 and their paramagnetic susceptibilities followed the Curie-Weiss law with the Weiss constant of 0±5°K in the temperature range between 77°K and room temperature. It was noted that in these complexes paramagnetism is dominated by the monopositive ion radical of the amine and not by the quinone part. In contrast to this, the complexes formed by combinations of p-phenylenediamine and tetramethyl-p-phenylenediamine with p-chloranil and p-bromanil had a composition of 1 : 1 and showed paramagnetic susceptibilities which varied with temperature according to the thermal equilibrium between magnetic and non-magnetic states. The thermal equilibrium is characterized by the activation energy determined by the interaction between the monopositive and the mononegative ion radicals of the components. The absorption spectra of 1 : 1 complexes showed a charge-transfer band in the near-infrared region, while those of 2 : 3 complexes did not. The activation energy obtained magnetically is discussed in relation to the appearance of the charge-transfer absorption band. The temperature dependence of the activation energy is also discussed.
Studies of Helical Aggregates of Molecules. II. The Sense of Twist in the Fibrous Aggregates from the Alkali Metal Soaps of Optically Active 12-Hydroxystearic Acid
Authors: Tachibana Taro , Kitazawa Shyoko , Takeno Hideko
Published: July 2006

Under an electron microscope, it was observed that the alkali metal soaps of 12-d(or l)-hydroxystearic acid separated out twisted fibers from various solutions. A symmetrical relationship regarding the sense of the twist was found between the soap fibers of the d-enantiomer and those of the l-enantiomer. In the case of the soap fibers of the d-enantiomer, the sense of twist was right-handed for the Li soap and left-handed for the Rb and Cs soaps. The Na- and the K- soap fibers produced both right-handed and left-handed fibers. A solvent effect with respect to the sense of twist was found for the fibers of the free acid and its Li soap. The cause of the twisting was discussed in connection with the structure and the growth process of the soap crystal.
Synthesis of Cyclic α-Amino Acids. IV. Syntheses of Adenine Nucleosides of 3-Amino-3-C-carboxy-3-deoxy-d-ribofuranose and 3-Amino-3-C-carboxy-3-deoxy-d-ribopyranose
Authors: Yanagisawa Hiroaki , Kinoshita Mitsuhiro , Nakada Saburo , Umezawa Sumio
Published: July 2006

9-(3′-Amino-3′-C-carboxy-3′-deoxy-β-d-ribofuranosyl)adenine (I) and 9-(3′-amino-3′-C-carboxy-3′-deoxy-β-d-ribopyranosyl)adenine (II) have been synthesized. They are the first examples of nucleoside-derivatives which have an α-amino acid structure in their furanose or pyranose ring. A masked derivative (VII) of α-d-erythro-pentofuranos-3-ulose was converted into a hydantoin derivative (IX), which was acetolyzed and then treated with dry hydrogen chloride to give an acylglycosyl chloride (XI). Condensation of this derivative with chloromercuri-6-benzamidopurine followed by hydrolysis afforded I. Treatment of the hydantoin derivative (IX) with methanolic hydrogen chloride followed by hydrolysis gave methyl 3-amino-3-C-carboxy-3-deoxy-α-d-ribopyranoside (XVII), which has been found to be identical with one of the isomers of methyl 3-amino-3-C-carboxy-3-deoxy-α-d-pentopyranoside previously reported. The 1-O-acetyl-3-N-benzoyl-2,4-di-O-benzoyl derivative of ethyl ester of this acid (XVII) was fused with 6-benzamidopurine in the presence of p-toluenesulfonic acid and followed by hydrolysis to afford II. Structural proofs for the new nucleoside-derivatives were obtained from their ultraviolet, infrared and nuclear magnetic resonance spectra.
The Condensation Reactions of Bivalent Sulfur Compounds-Copper(II) Complexes with Nucleophiles
Authors: Mukaiyama Teruaki , Narasaka Koichi , Maekawa Kazuo , Hokonoki Hisao
Published: July 2006

It was found that the bivalent sulfur compounds such as benzaldehyde diethylmercaptal, benzophenone diethylmercaptole, ethyl orthotrithioformate and benzyl methylsulfide, react with copper(II) salts of 1,3-dicarbonyl compounds, active methylene compounds or anisole, in the presence of cupric chloride, to give condensation or substitution products in good yields accompanied with carbon-sulfur bond cleavage. On the other hand, in the absence of cupric chloride, the bivalent sulfur compounds underwent no reaction and the starting materials were recovered. These results can be explained by assuming initial formation of active complexes from the bivalent sulfur compounds and copper(II).
The Resolution of N-Benzyloxycarbonyl-Dl-amino Acids Using Ephedrine
Authors: Oki Katsue , Suzuki Kuniyoshi , Tuchida Seiichi , Saito Tomoo , Kotake Hiroshi
Published: July 2006

The use of ephedrine has here been proposed to be of value in the direct resolution of racemic N-benzyloxycarbonylamino acids. By using a half equi-amount of natural (−)-ephedrine, N-benzyloxycarbonyl derivatives of β-methyl Dl-aspartate, Dl-leucine, Dl-methionine, and O-benzyloxycarbonyl-Dl-serine resulted, each in turn producing a salt of the respective d-isomer. On the other hand, Dl-isoleucine, erythro-β-methyl-Dl-leucine, threo-N,β-dimethyl-Dl-leucine, Dl-valine, and Dl-phenylalanine each produced a salt of each l-isomer with the same base. It should be better to protect, if possible, the third functional groups of three functional amino acids before the resolution. Each antipode of the optically active N-benzyloxycarbonylamino acid obtained above was also conveniently produced, in a high optical purity, by using (+)-ephedrine alternately. However, a few limitations on the desirable method of resolution have also been observed.
Studies on Pyrophosphates. I. A Selective Degradation of Pyrophosphates by Means of 2,6-Dichloroquinone N-Chloroimide
Authors: Chong Kyu-Jang , Pong Sheng-Shung , Hata Tsujiaki
Published: July 2006

Reaction of P1,P2-dialkyl pyrophosphate with alcohols or water in the presence of 2,6-dichloroquinone N-chloroimide (CQC) was studied. It was found that alkyl p-nitrophenyl phosphates are obtained in high yields by treating P1,P2-di-p-nitrophenyl pyrophosphate with alcohols in the presence of CQC. Similarly, alkyl phosphates are selectively produced by the reaction of P1,P2-dialkyl pyrophosphates with water in the presence of CQC. These reactions afford a new procedure for the selective degradation of P1,P2-dialkyl pyrophosphates, especially nucleoside pyrophosphates.
Phenylation with Phenyl Radical Generated from Phenylazotriphenylmethane
Authors: Kobayashi Michio , Minato Hiroshi , Watanabe Nobuko , Kobori Nobumasa
Published: July 2006

Phenylazotriphenylmethane was decomposed in substituted benzenes, and orientations and partial rate factors for phenylation were determined.
Effect of Coexisting Minerals on the Graphitization of Carbon under Pressure. IV. Accelerating Effect of Calcium Oxide
Authors: Hirano Shin-ich , Saito Hajime , Inagaki Michio
Published: July 2006

Heat treatments of polyvinylchloride coke in the presence of three kinds of calcium oxide calcined at different temperatures were carried out in order to study the effect of the reactivity of calcium oxide on the acceleration of graphitization of carbon under the quasihydrostatic pressure of 3.2 kbar. A remarkable difference in the accelerating effect on graphitization was confirmed. In the presence of the most reactive calcium oxide calcined at 920°C, the graphitization of the carbon began at about 1100°C and the content of the graphitic component became 100% by heat treatment at 1500°C for 60 min. While in the presence of the least reactive calcium oxide calcined at 1470°C, the graphitic component, an even hump on the corresponding diffraction angle, could not be detected in specimens heat-treated below 1500°C. The content of graphitic component and the distribution of calcium in heat-treated specimens were measured by an electron microprobe analyzer. It was found that the part having a larger content of calcium had a larger content of the graphitic component. A possible mechanism of the accelerating effect of calcium compound on graphitization is considered to be chemical concerning the intermediate formation of carbide or metal. The formation of the graphitic component seems to proceed by the reaction:

CaO+C (amorphous)→Ca+CO→CaO+C (graphite)\labeleq1

below 1300°C, and above 1300°C, mainly by the reaction:

CaO+3C(amorphous)→CaC2+CO→CaO+3C (graphite)\labeleq2

and also by reaction (1). The driving force of the formation of the graphitic component through these reactions is the difference in the free energy between amorphous carbon and graphite, viz., disordered and ordered graphite.
Photoreduction of Phenazine in Alcohols and by EDTA in the Aqueous Solution
Authors: Iwaoka Teiki , Niizuma Shigeya , Koizumi Masao
Published: July 2006

By the combined use of the steady-light experiment and a flash technique, photoreduction of phenazine in methanol, ethanol, isopropanol and by EDTA in the aqueous solution and also the related elementary processes have been studied. The photoproduct has been identified as dihydrophenazine of which the absorption spectrum has been measured for the first time. It has been concluded that the lowest triplet, T(π–π*) is not a reactive state. Most probably the reactive state is a higher T(n−π*). The quantum yields of photoreduction in methanol, ethanol, and isopropanol are respectively 0.023, 0.037 and 0.050. Singlet-Triplet transition probability (ΦST) has been found to be >0.33 in the aqueous solution. Semiquinone produced in alcohols disappears by disproportionation reaction with almost the diffusion controlled rate constant while in the aqueous solution the disproportionation is much slower and at high EDTA concentrations, semiquinone is further reduced by EDTA. The absorption due to a molecular compound consisting of phenazine and dihydrophenazine has been detected in the visible region. It has been suggested that a certain equilibrium exists between three compounds and that a rather stable radical species, the existence of which has been proved by an ESR spectroscopy, participates in this equilibrium.
The Hydrated and Anhydrous Copper(II) Complexes with Thioglycolic Acid Derivatives
Authors: Ohashi Yayoi , Takeuchi Toshio , Ouchi Akira , Yoshino Yukichi
Published: July 2006

The dihydrates and anhydrous copper(II) complexes with methyl, ethyl, n-propyl, isopropyl, n-butyl, and benzyl thioglycolic acids were synthesized, and their properties were investigated. The magnetic data show that the copper in the complexes is divalent and that the complexes do not have a copper(II) acetate structure. The spectroscopic data show that these ligands bond to the central metal ion as strongly as does amino acid or water. In the case of isopropyl thioglycolato copper(II) dihydrate, the blue and the violet isomers were obtained. The structures of the complexes in the solid state as well as in the solution were discussed.
The Polymerization of Di-(β-methacrylyloxypropionaldehyde)-pentaerythritolacetal
Authors: Ouchi Tatsuro , Imase Yorihiro , Oiwa Masayoshi
Published: July 2006

The polymerization of di-(β-methacrylyloxypropionaldehyde)-pentaerythritolacetal (Dβ-MPP) and the copolymerizations of DβMPP with styrene (St) and acrylonitrile (AN) have been carried out at 60°C, using benzoyl peroxide as an initiator. They have then been discussed kinetically from the point of view of cyclopolymerization. The results can be summarized as follows:

1) The relation among the rate of polymerization, Rp, the initiator concentration, (I), and the monomer concentration, (M), can be expressed by the following equations;

& R_p/(I)^1/2=A(I)^1/2+B

& R_p/(M)=C(M)+D

where A, B, C, and D are constant.

2) The ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized radical, kc⁄kp, was 22.0 mol/l.

3) The copolymerization of DβMPP proceeded primarily by means of cyclocopolymerization, and the ratio of the cyclization rate to the vinyl propagation also decreased with an increase in the comonomer fraction in the copolymer.

4) The following reactivity ratios were estimated on the basis of the Smets-Roovers equation: (Remark: Graphics omitted.)
1,2-Dithiole-3-thione and 1,2,4-Trithiole from α-Cyanodithiocarboxylate
Authors: Yokoyama Masataka
Published: July 2006

1,2-Dithiole-3-thiones and 1,2,4-trithioles were synthesized by the reaction of α-cyanodithiocarboxylate, hydrogen sulfide, and bromine water. The reaction mechanism and the mass spectra of 1,2-dithiole-3-thiones were discussed.
Kinetic Studies of the Pulse Radiolysis of trans-Stilbem in Several Solvents
Authors: Ueda Hisashi
Published: July 2006

The kinetics of the transient species of trans-stilbene in several solvents were studied using single pulsed electron beam (0.5 μsec×300 mA) and the spectroscopic method. The species existing immediately (0–20μsec) after a pulse is found to disappear according to a sum of two first-order decay-rate equations. The temperature dependence of the formation and decay of this species shows that there are two different trans-stilbene cations, Rs and Rf, which have almost identical absorption spectra but different formation and decay rates. The rate constants for Rs were not affected by the temperature, however, those for Rf were strongly affected. Rf is not found in the solution of trans-stilbene in 1,2-dichloroethane if a small amount of CCl4 is added. Some effects of the dielectric constant were observed on the decay-rate constant of Rf. From these facts, it can be concluded that Rf is formed by an ordinary transfer of a hole from the solvent cation to the solute molecule. As Rs seems to be formed by a mechanism other than that of Rf, a possible scheme for it has been discussed.
The Structure Theory of Water. III. The Order-Disorder Theory
Authors: Arakawa Kiyoshi , Sasaki Katsutaka
Published: July 2006

Taking into account the cooperative nature of cluster formation, we applied the order-disorder theory, using Bragg and Williams’s approximation, to liquid water based on a two state model. The two state model consists of hydrogen-bonded molecules arrayed on α-sites in a tetragonal lattice and non hydrogen-bonded molecules on β-sites in the lattice. A partition function was formulated and calculated. The calculated energy difference, ε, between the molecules on β-sites and those on α-sites decreased continuously with the rise of temperature. Thermodynamic variables of liquid water were calculated at each temperature, where no adjustable parameter was used. Agreement between calculated values and observed ones is fairly good.
Radiotracer Studies on Adsorption of Surface Active Substance at Aqueous Surface. II. The Effect of Excess Salt on the Adsorption of Sodium Dodecylsulfate
Authors: Tajima Kazuo
Published: July 2006

The adsorbed amount and the surface tension at the air-solution interface of the solution of tritiated sodium dodecylsulfate in the presence of excess common inorganic salt have been accurately measured at 25°C. The radioactivity of tritium β-rays over the solution was counted with a sheet scintillation counter and the surface tension of the solution was measured by a drop volume method. In the sodium dodecylsulfate solution containing sodium chloride of 0.115 mol/l, the adsorbed amount of dodecylsulfate ions was saturated to give 4.33×10−10 mol/cm2 when the bulk concentration was higher than 5.0×10−4 mol/1000 g solution. In the presence of the excess inorganic salt common to the ionic surfactant in solution the Gibbs adsorption isotherm has been experimentally proved to be valid for n=1. Moreover, it was confirmed that the equation of state for the ionic adsorbed film on the salt-free solution proposed previously is also applicable to the ionic surfactant solution with the excess salt.
The Fractionation of Tritium in the Crystallization of Inorganic Hydrates from a Tritiated Solution
Authors: Tanaka Haruhiko , Negita Hisao
Published: July 2006

Bennema’s theory of crystal growth from a solution was modified and used in explaining fractionations of tritiated water in the crystal-growth processes of several inorganic hydrated salts from concentrated aqueous solutions. It was suggested that some water molecules in the aqueous solutions were free to become growth units which are not necessarily activated for entering the crystal surface. The dilution of tritiated water in the crystal was observed; this was explained in a satisfactory way in terms of the surface-diffusion model originally proposed by Burton, Cabrera, and Frank. On the contrary, the volume diffusion model was inadequate for interpreting the fractionation of tritium.
Organic Charge Transfer Salts; Absorption Spectra of Salts between the Pyrylium or Thiopyrylium Cation and the 1,1,3,3- Tetracyanopropenide or Tricyanomethanide Anion
Authors: Yasuba Hiroshi , Imai Tatsuro , Okamoto Kenichi , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

New organic charge transfer salts composed of an organic cation (pyrylium or thiopyrylium) and an organic anion (1,1,3,3-tetracyanopropenide or tricyanomethanide) were prepared. The absorption spectra were studied both in solution and in a solid. These salts have the charge transfer band in the visible region as a result of the electronic transition from the anion to the cation. The charge transfer bands of these salts in solution are sensitive to the nature of the solvent. The charge transfer band is observed in solvents with a low polarity; this band shifts toward a shorter wavelength in solvents with a high polarity. The increase in the polarity of the solvent causes a decrease in the apparent molar extinction coefficient. The charge transfer band in the solid shifts toward a shorter wavelength compared with that in the solution. In a single crystal, the polarized absorption spectrum shows a remarkable dichroism.
The Crystal and Molecular Structure of Bromoanhydrotetrodoic Lactone Hydrobromide
Authors: Furusaki Akio , Tomiie Yujiro , Nitta Isamu
Published: July 2006

The absolute configuration of bromoanhydrotetrodoic lactone, C11H14O7N3Br, has been determined on the basis of an X-ray study of its hydrobromide. The crystals are orthorhombic, with four chemical units in a unit cell of these dimensions: a=10.88±0.04, b=15.95±0.05, and c=8.55±0.03 Å; the space group is P212121. The observations for Bijvoet inequalities were made on equi-inclination integrating Weissenberg photographs taken with CuKα radiation around the a axis. On the other hand, the calculations were carried out with the parameters at the stage of the R factor of 11.9% and with anomalous dispersion correction of −0.9 for Δf′Br and 1.5 forΔf″Br . The observed and calculated inequalities for ten pairs of reflections were all in agreement with each other, so the absolute configuration was determined without any uncertainty. In addition to the X-ray determination of the absolute configuration mentioned above, the present paper will describe the details of the crystal and molecular structure.
The π-Electronic Structures of Five-membered Heterocycles Containing Two or Three Heteroatoms and Their Benzo-derivatives
Authors: Kamiya Mamoru
Published: July 2006

The semiempirical Pariser-Parr-Pople SCF method combined with configuration-interaction has been applied for calculation of the electronic spectrum, ionization potential and electron affinity, π-electron distribution and total π-energy of such heterocycles as oxazole, isoxazole, oxadiazoles, imidazole, pyrazole, triazoles and their monobenzo-derivatives, and the theoretical results have been compared with the available spectral data and miscellaneous chemical properties including the position-dependency on substitution reactions, novel photochemical isomerization of several compounds and so forth.
The Diffuse Reflection Spectra of 1-Arylazo-2-naphthols Diluted with Sodium Chloride
Authors: Dehari Chihiro , Matsunaga Yoshio , Tani Kensuke
Published: July 2006

The diffuse reflection spectra of sixteen 1-arylazo-2-naphthols diluted with sodium chloride were measured at concentrations of 1, 0.1, and 0.01% in the range from 350 to 700 mμ. The spectra indicate the coexistence of the azo and hydrazone tautomers in this solid, two-component system. Moreover, the spectra were found to be markedly modified in many cases by elevating the temperature, especially at a concentration of 0.01%. These changes were shown to be thermally reversible and were attributed to the movement of the tautomeric equilibrium. The direction depends upon the kind and position of the substituents, e.g., towards the hydrazone tautomer in the case of the p-Cl and o-NO2 derivatives and towards the azo tautomer in the case of the p-NO2 and o-OH derivatives. It was suggested that the present systems are not simple mixtures of pulverized 1-arylazo-2-naphthols and sodium chloride, but that some fraction of the organic components is well dispersed and adsorbed on the highly polar surface of the alkali halide.
Electronic Structures of Aromatic Ketyl Radicals and Related Hydrocarbon Radicals
Authors: Kanamaru Nobuaki , Nagakura Saburo
Published: July 2006

The π-electron structures of neutral aromatic ketyl radicals and their related hydrocarbon radicals were studied theoretically by combining the open-shell SCF MO method with the configuration-interaction calculation. The observed absorption bands of these radicals were well explained by the present theoretical study. From a comparison of the calculated transition energies and intensities with the observed values, it was concluded that the longest and second longest wavelength bands of the benzyl radical and the second longest wavelength band of the diphenylmethyl radical shift to shorter wavelengths upon hydroxy substitution. This may be regarded as characteristic of the substituent effect upon the absorption bands of aromatic radicals. The calculated spin densities were found to be consistent with the reactivity of the ketyl radicals in the formation of pinacols.
Studies of Acenaphthene Derivatives. XX. The Reactions of Benzylideneacenaphthenones with Sulfonium Ylides
Authors: Tsuge Otohiko , Shinkai Ichiro
Published: July 2006

The reactions of benzylideneacenaphthenones with sulfonium ylides were studied extensively. Although the reactions of benzylidene- and p-methylbenzylideneacenaphthenone with dimethylsulfonium methylide gave only resinous materials, the p-chlorobenzylidene derivative condensed with the ylide to afford the corresponding spiroxirane compound in a good yield. In the reactions with dimethyloxosulfonium methylide and carbonyl-stabilized sulfonium ylides such as ethyl (dimethylsulfuranilidene) acetate and dimethylsulfonium phenacylide, benzylidene-acenaphthenones gave the corresponding spirocyclopropyl ketones in good yields. The products obtained in the latter reactions were established to be cis-cyclopropyl compounds on the basis of NMR spectral studies. On the other hand, ethoxycarbonylmethyleneacenaphthenone condensed with carbonyl-stabilized sulfonium ylides to give trans-cyclopropyl ketones. On the basis of these results, the reaction mechanism was discussed. Also, bis-2,2′-methyleneacenaphthenone reacted with ethyl (dimethylsulfuranilidene) acetate to give the bis-spirocyclopropyl ketone.
The Preparation, Lithium Aluminum Hydride Reduction, and Electronic Spectra of Halogen-substituted 3,4-Bis(diphenylmethylene)-cyclobutenes and -cyclobutanes
Authors: Toda Fumio , Kumada Kunihiro , Ishiguro Nobuo , Akagi Katsuhiko
Published: July 2006

The title compounds were prepared, and their physical and chemical properties were investigated. The reduction of the cyclobutenes with lithium aluminum hydride afforded halogenfree cyclobutane. The mechanism of the reduction is discussed. The cyclobutenes showed their K-bands in a wavelength region ca. 100 nm shorter than in the cases of the corresponding cyclobutanes. Furthermore, the K-band of the cyclobutenes is comparable to that of 1-phenylbuta-1,3-diene. On the basis of the electronic spectral data, a puckered structure was postulated for the cyclobutenes.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. II. The Synthesis and the Electronic Spectra of 9,9′ -Dianthrylpoly-ynes
Authors: Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

A series of 9,9′-dianthrylpoly-ynes (II1–II6) were prepared, and their electronic spectra were measured. It was found that the novel linear relation between λmax and the square of the number of the triple bond (n2) which has been found in the spectra of 1,1′-dianthrylpoly-ynes (I1–I6) also held in the 9,9′-series.
Aminocyclitols. XXIV. Synthesis of Inosamines from Bromodeoxyinositols
Authors: Suami Tetsuo , Ogawa Seiichiro , Uchida Masaru
Published: July 2006

Seven inosamines (scyllo, chiro-1, myo-2, myo-4, allo-5, neo-1 and chiro-3) have been prepared from four bromodeoxyinositols [scyllo, chiro-1, allo-5 and neo-1). When bromodeoxyinositols were treated with sodium azide in boiling aqueous 2-methoxyethanol or dimethylformamide, followed by acetylation, pentaacetyl azidodeoxyinositols were obtained in 60–80% yield. On catalytic hydrogenation using Adams’ platinum oxide, the azido compounds yielded hexaacetyl inosamines in good yields. Proton magnetic resonance (PMR) spectra of acetyl azidodeoxyinositols have been studied.
The Effect of Solvents on the Optical Rotation of Poly(propylene Oxide)
Authors: Kumata Yoshiyuki , Furukawa Junji , Fueno Takayuki
Published: July 2006

The change in the rotatory direction of optically active poly(propylene oxide) in different solvents has been discussed from the viewpoint of dielectric theory of solution. It has been pointed out that, in general, the shapes of the optical rotatory dispersion curves of polymers cannot directly be related to their conformation.
The Phase Transitions of the Anion Radical Salts Containing Mixed Cations; [(C6H5)3PCH3]1−x+[(C6H5)3AsCH3]x+(TCNQ)2\ewdot, (0≤x≤1)
Authors: Iida Yôichi
Published: July 2006

The phase transitions of the anion radical salts containing mixed cations represented by [(C6H5)3PCH3]1−x+[(C6H5)3AsCH3]x+(TCNQ)2\ewdot, (0≤x≤1) were investigated. The transition temperature, Tc, and the magnitude of the heat, ΔH, of the transition were determined as a function of the composition parameter, x, by means of a differential scanning calorimeter. It was found that Tc increases, and ΔH decreases, monotonously with an increase in the value of x, and that the phase transition disappears with x=1.00. The mechanism of the phase transitions was discussed on the basis of the theory of triplet exciton-exciton interaction proposed by Chesnut. The theoretical values of the entropy changes of the transitions were found to be much less than those observed. In view of these results, it was concluded that the anomalies in the magnetic susceptibilities of these salts were induced by the change in the crystal structure.
Phosphorus Nuclear Magnetic Resonance in Polyphosphates and Determination of Their Hydrolysis Rate Constants
Authors: Kawabe Makoto , Ohashi Osamu , Yamaguchi Ichiro
Published: July 2006

The phosphorus nuclear magnetic resonance spectra of several condensed phosphates (polyphosphates) were measured in aqueous solutions. The NMR spectra generally consist of three peaks which correspond to the phosphorus atoms at the end and middle of the molecular chain and in orthophosphoric acid which is the final product of the hydrolysis. The chemical shift and, for some phosphates, spin-spin coupling constants were obtained. Both depend on pH of the solution. The chemical shifts for the end and middle phosphorus atoms depend also on the chain length of the molecule. The hydrolysis process of the phosphates can be traced by the observation of the time dependence of spectral line intensities. From this observation the rate constant of the hydrolysis is obtained for several phosphates. The values are comparable with those obtained by other methods.
An Infrared Spectroscopic Study of Hydrogen Bonding Interaction. Structural Studies of Proton-donating and -accepting Powers
Authors: Kagiya Tsutomu , Sumida Yūzō , Tachi Toshihiro
Published: July 2006

The relationship between the proton-donating and proton-accepting powers and the structures of various proton donors and acceptors was studied in the liquid phase by means of an infrared spectrophotometer. The proton-donating powers of the donors were evaluated by means of the ratios of the O–H shifts of the donors (RO–H) to those of methanol in various proton acceptor solutions. The proton-accepting powers of the acceptors were evaluated by means of the division of the O–H shifts by the proton-donating powers of the donors used. The proton-donating powers increased with the decrease in the pKa or the ionic RO–H bond dissociation energies and with the increase in the electron affinities of RO radicals, i. e., t-butanol<methanol<<trimethylsilanol<phenol<p-nitrophenol. In a homologous series, the proton-accepting powers increased with the decrease in the ionization potentials. In the case of the aromatic ethers with two proton accepting sites, two characteristic O–H vibrational bands were observed. The difference in the protonaccepting powers of the vinyl and ethyl compounds with the same substituent was observed, and the π-electron-mobility index, which was considered to be a measure of the energy level of the π-electrons of the vinyl group, was defined and discussed.