bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxidation of s-Butyl Alcohol by Cerium(IV)
Authors: Mathur D L , Bakore G V
Published: July 2006

The oxidation of s-butyl alcohol by Ce(IV) in dilute nitric acid medium has been studied. The reaction is of first order with respect to Ce(IV)but of fractional order with respect to s-butyl alcohol. A plot of inverse of alcohol concentration against inverse of observed first order rate constant gave a straight line which did not pass through the origin. This suggests an intermediate Ce(IV)-alcohol complex formation. By repeating this procedure at different temperatures the formation constants of the complex and the thermodynamic parameters for the complex formation process have been evaluated. Hydrogen, nitrate, and sulphate ions decrease the rate of oxidation. The results have been explained on the basis of equilibrium Ce4++H2O\oversetKh\ightleftarrows Ce(OH)3++H+ and assuming Ce(OH)3+ as the reactive species of Ce(IV). From the slope-intercept of straight line obtained between inverse of observed rate constant and [H+], value of Kh=6.19 at 35°C has been evaluated in dilute nitric acid at μ=2.55 m. A mechanism in which the first step is the rapid reversible formation of a complex between Ce(IV) and Substrate followed byα–C–H bond rupture in the rate determining step has been suggested.
A Theoretical Consideration of the Electron-scavenging Process in Liquid Hydrocarbons. II. Pulse Irradiation
Authors: Yamazaki Hideo , Shinsaka Kyoji
Published: July 2006

A mathematical treatment of the electron recombination process is presented on the basis of the extended Smoluchowski equation, which includes the effects of several positive ions as ion cores in a spur and of a scavenger. The equation is reduced to the usual Smoluchowski equation for the geminate recombination in a special case. The time dependence of the electron concentration is obtained using a successive approximation. The results of numerical calculations for various reaction parameters are presented.
Gel Filtration of Aqueous Sodium Dodecyl Sulfate
Authors: Suzuki Hitoshi , Sasaki Tsunetaka
Published: July 2006

Gel filtration of an aqueous solution of sodium dodecylsulfate (SDS) was carried out using Sephadex G-50 as a gel column, and the overall elution rate (Rf) of SDS was measured. The value of Rf was found to be independent of the concentration C of SDS below a certain point, above which it increased with increasing C. A sharp break point observed coincided with the critical micelle concentration (CMC) of SDS. The intermicellar concentration of SDS was estimated from the shape of the elution curve for the solutions beyond CMC, and shown independent of the total concentration C. The value of Rf for the micelle was further determined by direct measurement. The value was found to increase slightly with C above CMC, becoming practically constant above about 1.4×10−2 mol/l. It was concluded from the results that the size of the micelle also increase with the concentration above CMC. Theoretical equations were derived for the relation between Rf and C below and above CMC. Observed Rf  vs.  C relation fitted the equations satisfactorily, from which CMC was calculated. A rapid equilibrium between micelles and monomer ions and the independence of intermicellar concentration on C were also confirmed.
Electron Spin-Spin Interaction in the Multiplet Ground State of Non-planar Methylene Derivatives
Authors: Higuchi Jiro
Published: July 2006

The effect of deviation from the planar structure in electron spin-spin interaction has been semiempirically investigated for spin multiplet ground state of radicals with methylene bonds. If these bonds are not coplanar, a significant influence occasionally appears on the values of D and E, while the influence is very small if the relative orientation among the methylene bonds still does not change.
A Further Study of the Scavengeable Electron Yield in the Radiolysis of Hydrocarbon Glasses at −196°C
Authors: Kimura Toyoaki , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

The yield of scavengeable electrons produced by γ-irradiation in mixtures of cyclopentane and methylcyclohexane at −196°C has been determined by electron-scavenging experiments with bromobenzene. It has been found that the maximum yield of scavengeable electrons in these mixture glasses increases with an increase in the cyclopentane concentration and that it reaches the total ionization yield in a liquid hydrocarbon. The implication of these results for the yield of radiation-induced ionization in condensed systems is discussed.
The Decomposition of Energized Ethylene Formed in the Photolyses of Alkanes
Authors: Ogata Yuji , Obi Kinichi , Akimoto Hajime , Tanaka Ikuzo
Published: July 2006

The decomposition and the collisional deactivation of energized ethylene formed in the photolyses of ethane, propane, n-butane, and cyclobutane at 1470 Å have been studied from the change in ethylene and acetylene yields with varying pressures of alkane or nitrogen added as a deactivator. The rate constants of the collisional deactivation and decomposition of energized ethylene were determined from the experimental data. The unimolecular decomposition theory has been applied to energized ethylene, and the results compared with the experimental rate constants.
ESR Studies of Methyl Radicals Stabilized on Silica-gel Surfaces
Authors: Kubota Shozo , Iwaizumi Masamoto , Isobe Taro
Published: July 2006

The methyl radicals produced on silica-gel surfaces by the photolysis of methyl iodide or methane have been investigated by ESR. When the silica gel is preheated at high temperatures (above ca. 300°C), two methyl radicals which have abnormally small hfs constants are trapped on the surfaces. In the case of the photolysis of methyl iodide, these two radicals disappear by continuing uv-irradiation, and instead an ordinary type of methyl radical is produced. The former two radicals have nearly isotropic g-values, and these values are approximately equal to that of a free electron and are considered to have a non-planar structure. The adsorption sites for these radicals were estimated to be siloxane groups. On the other hand, when the silica gel is preheated at low temperatures (below ca. 300°C) the methyl radicals produced have hfs constants of the same magnitude as that of the ordinary type of methyl radical, but each proton line of the radicals is accompanied by four satellite lines. The outer satellite lines have been confirmed by measurements of the X- and K-band spectra to be a concurrent spin-flip transition of an odd electron and a nearby proton of the silica-gel surface. The models of the adsorption state of the radicals are considered.
The Separation of Aluminum from Iron by the Zone-melting of Their Complexes
Authors: Mashima Michio , Maruyama Kazuo
Published: July 2006

The separation of Al from Fe was attempted as a first step in the chromatographic application of the zone-melting method to metal complexes. N,N′-ethylenedianthranilic acid and benzoic acid complexes, and various organic solid solvents were prepared. The experiment was carried out with a zone speed of 6 cm/hr and a moltenzone length of 0.6–1.0 cm at 75°C. When stearic acid was used as the solvent, the recovery percentage of Al was about 75% with the benzoic acid complex and about 99% with the N′ N′-ethylenedianthranilic acid complex. Furthermore, the effective distribution coefficient and phase diagram supported due idea of the behavior of the complexes.
Studies of Aliphatic Hydroxycarboxylic Acids as Antioxidant. V. Complexes of Copper(II) with erythro- and threo-2-Methyltartaric, and meso- and threo-2,3-Dimethyltartaric Acids
Authors: Horikawa Kazuo , Masuyama Shinroku
Published: July 2006

The dissociation constants of erythro- and threo-2-methyltartaric and meso- and threo-2,3-dimethyltartaric acids were determined by the potentiometric titration method at the ionic strength of μ=0.1 and at 22°C. The values of the dissociation constants were pK1=3.54 and pK2=5.03 for erythro-2-methyltartaric acid, and pK1=3.28 and pK2=4.70 for the threo-form. For meso-2,3-dimethyltartaric acid, the corresponding values were 3.52 and 4.98, while the threo-form had values of 3.04 and 5.30. The complex formation of copper(II) with these acids has been investigated using Job’s method of continuous variations at the ionic strength of μ=0.2 and at 22°C. Copper-(II) and erythro-2-methyltartaric acid react in a 1 : 1 ratio at pH 2.40 and in a 3 : 2 ratio at pH 5.00. On the other hand, the threo-form does not combine with copper(II) at pH 2.40, though it does react at pH 5.00 in a 1 : 1 ratio. As for meso-2,3-dimethyltartaric acid, the complex formation in a 3 : 2 ratio was observed at pH 5.00. However, the threo-form and copper(II) react in a 1 : 2 ratio at pH 5.00. The equilibrium constants (apparent stability constants) were calculated by the method of Turner and Anderson. The values of the equilibrium constant were log K=9.71 (pH 5.00) and log K=2.02 (pH 2.40) for erythro-2-methyltartaric acid, log K=3.78 (pH 5.00) for the threo-form, log K=9.70 (pH 5.00) for meso-2,3-dimethyltartaric acid, and log K=5.19 (pH 5.00) for the threo- form. On the basis of these data, the structures of these complexes are discussed.
The Chelate Formation of (o-Substituted Phenylazo)chromotropic Acids with Alkaline Earth Metals. II
Authors: Katayama Takeshi , Miyata Haruo , Tôei Kyoji
Published: July 2006

The acid dissociation constants of phenylazochromotropic acid and its o-substituted derivatives with -CH3, -OCH3, -COCH3, -COOH, -CH2COOH, -COCOOH, -OCH2COOH, and -CH(OH)COOH in the ortho position to the azo group, and the stability constants of their 1 : 1 metal chelates with alkaline earth metals have been measured by potentiometric titation. The measurements have been carried out at 25°C and at μ=0.10 with KNO3. The effects of these substituents on the acid dissociation constants of the reagents and on the stability constants of these chelates were discussed. The pKa value for the naphtholic proton of the o-substituted reagents was larger than that of phenylazochromotropic acid, and the stability constants of these chelates with alkaline earth metals decreased as follows: Mg>Ca>Sr>Ba, while for the chelates of the o-OCH2COOH reagent the order was Ca>Mg>Sr>Ba, and for the o-CH(OH)COOH reagent it was Mg≈Ca>Sr>Ba. The plots of the stability constants, log K1 against the sum of the acid dissociation constants, pKA(=pKa1+pKa2), were approximately linear except for the above two reagents with calcium, strontium, and barium. From the results obtained, the o-OCH2COOH reagent that behaves as a quadridentate ligand forms a more stable chelate with calcium, strontium, and barium, and the effect of the -OCH2COOH group, especially that of the coordination of the -O- atom, is remarkable in its calcium chelate.
The 3020-cm−1 Band in the Infrared Absorption Spectra of Methyl Esters of Unsaturated Higher Fatty Acids
Authors: Hirabayashi Yoshio , Kato Nobukatsu , Mizuta Masateru , Ishihara Hideharu
Published: July 2006

Studies were made of the infrared absorption spectra of methyl esters of oleic, elaidic, linoleic, linoelaidic, trans-10, cis-12-octadecadienoic, α-eleostearic, stearolic, stearic, 9,10-dideutero-oleic, and 9,10-dideutero-elaidic acids in the C–H stretching region. It was further confirmed that the prominent absorption bands at 3020 cm−1 occurring in the infrared absorption spectra of methyl esters of unsaturated higher fatty acids are assignable to the =C–H stretching vibrations of a cis-ethylenic double bond. The =C–D stretching vibrations of deuteroethylenic double bonds (–CD=CD–) in methyl 9,10-dideutero-oleate and -elaidate occurred at 2250 and 2225 cm−1 respectively.
The Stereochemistry of the Reduction of 2-Substituted Cyclopentanones with Complex Aluminum Hydrides
Authors: Senda Yasuhisa , Mitsui Sekio , Ono Ryuko , Hosokawa Shizuo
Published: July 2006

Five different 2-substituted cyclopentanones have been reduced by complex aluminum hydrides in various solvents. In the lithium aluminum hydride reduction, the proportion of cis 2-substituted cyclopentanols tends to increase with the steric bulkiness of the substituent. The fact that the composition of the products changes with the sort of solvent is discussed in terms of the difference in the coordinating abilities of the solvents. More cis 2-substituted cyclopentanols are obtained by lithium trimethoxyaluminum hydride than by the other complex aluminum hydrides used in the present study. Lithium tri-t-butoxyaluminum hydride and lithium aluminum hydride-aluminum chloride reduction are also investigated.
Synthesis and Decomposition of Alkane- and Arenesulfonyl Aryl Disulfides
Authors: Abe Yasuo , Nakabayashi Takeshige , Tsurugi Jitsuo
Published: July 2006

Pyridinium alkane- and arenethiolsulfonates were allowed to react with arenesulfenyl chlorides, CISAr′, to yield sulfonyl disulfides in which R is n-dodecyl, benzyl, phenyl, or p-tolyl group, and Ar′ o-nitrophenyl or o-nitro-p-chlorophenyl. p-Toluenesulfonyl p-nitrophenyl disulfide was also prepared by this method. IR and UV spectra of these compounds were determined and compared with those of the corresponding thiolsulfonates. Decomposition of 35S-labeled p-toluenesulfonyl p-nitrophenyl disulfide, p-CH3C6H4SO2S35SC6H4NO2-p, gave 35S-labeled p-nitrophenyl p-toluenethiolsulfonate, p-CH3C6H4SO235SC6H4NO2-p. Triphenylphosphine was found to attack two oxygen atoms and a sulfur atom of p-toluenesulfonyl o-nitrophenyl disulfide at the same rate. The reaction of triphenylphosphine with 35S-labeled p-toluenesulfonyl o- and p-nitrophenyl disulfides revealed that the central sulfur atom of these sulfonyl disulfides was desulfurated. This result coincides with that of the decomposition mentioned above. The susceptibility of sulfonyl disulfides containing p-nitrophenyl group to the decomposition and the desulfuration of the central sulfur atom of sulfonyl disulfides in general are also discussed.
The Total Synthesis of (±)-Taxodione, A Tumor Inhibitor
Authors: Matsumoto Takashi , Tachibana Yakudo , Uchida Junji , Fukui Kenji
Published: July 2006

A total synthesis of (±)-taxodione (I) has been achieved. The Friedel and Crafts reaction of 1,2-dimethoxy-3-isopropylbenzene (IV) with succinic anhydride gave β-(4-hydroxy-3-isopropyl-5-methoxybenzoyl)propionic acid (V), which was then converted to γ-(4,5-dimethoxy-3-isopropylphenyl)butyric acid (IX). Since the cyclization of IX gave 6,7-dimethoxy-8-isopropyl-1-tetralone (X), the acid (IX) was subjected to bromination, cyclization, and then debromination. Subsequently, 7,8-dimethoxy-6-isopropyl-1-tetralone (XIII) was converted to (±)-7,8-dimethoxy-6-isopropyl-1-methyl-2-tetralone (XV). The condensation of (±)-XV with the methyl vinyl ketone gave a (±)-hexahydro-2-oxo-phenanthrene derivative (XVI), which was then further converted to (±)-11,12-dimethoxyabieta-5,8,11,13-tetraene (XIX). The introduction of a carbonyl group at the 6 position was achieved by the hydroboration of (±)-XIX, followed by the oxidation of the resulting 6-hydroxyl derivative. Finally, (±)-11,12-dimethoxyabieta-8,11,13-trien-6-one (XXI) was converted to (±)-I, whose IR, UV, and NMR spectra were identical in every respect with those of natural taxodione.
The Hofmann Rearrangement. IV. Kinetic Isotope Effect of N-Chlorobenzamide
Authors: Imamoto Tsuneo , Kim Seung-Geon , Tsuno Yuho , Yukawa Yasuhide
Published: July 2006

Kinetic isotope effects in the Hofmann rearrangement of phenyl-1-14C and carbonyl-14C labeled N-chlorobenzamides were measured in a sodium hydroxide solution at 15°C. The observed isotope effect on the phenyl-1-carbon is

k 12⁄k14=1.0456±0.0012

and that on carbonyl-carbon is

k 12⁄k14=1.0447±0.0006

These results strongly support a concerted mechanism for this rearrangement. Attempts have been made to correlate the isotope effect on phenyl-1-carbon to the r-value of the linear aromatic substituent-reactivity relationship in related 1,2-rearrangements.
Synthetic Studies of Amino Acids by the Use of Copper Complex. II. The Condensation Reaction of N-Pyruvylideneglycinatocopper(II) Complexes with various Aldehydes
Authors: Ichikawa Tetsuya , Maeda Sadao , Okamoto Toshiro , Araki Younosuke , Ishido Yoshiharu
Published: July 2006

An investigation of the mechanism of the reaction which involves the base-catalyzed condensation of bis(glycinato)copper(II) with aldehydes was carried out with the purpose of improving it so that it can proceed even with lower molar equivalent ratios of aldehydes to the complex and under milder conditions. On the basis of the results reported in the literature and those of this investigation, the reaction has been carried out as expected and has been newly shown to be applicable to p-tolualdehyde and p-chlorobenzaldehyde, and, moreover, to such aldehydo sugar derivatives as 2,3-O-isopropylidene-d-glyceraldehyde by the use of N-pyruvylideneglycinatocopper(II) complexes in the reaction in place of bis(glycinato)copper(II). An attempt at further improvement will also be described in the present communication.
Studies of Hydroxy Amino Acids. I. Separation of Diastereoisomers of Threonine
Authors: Ariyoshi Yasuo , Sato Naotake
Published: July 2006

It was found that Dl-allothreonine forms scarcely any soluble compounds with 5-nitronaphthalene-1-sulfonic acid, α-naphthylphosphoric acid, chlorendic acid, and tetrachlorophthalic acid in water. Dl-Threonine formed soluble or unstable compounds in water with these acids. The synthetic threonine mixture was successfully separated into Dl-threonine and Dl-allothreonine.
Chemically Induced Dynamic Nuclear Polarization in the Photochemical Reaction of Phenanthraquinone with Hydrogen Donors. II. A Consideration of Unusual Nuclear Spin Polarization
Authors: Shindo Heisaburo , Maruyama Kazuhiro , Otsuki Tetsuo , Maruyama Tetsuo
Published: July 2006

Polarized quartet NMR signals due to methylene protons were observed in the hydrogen-abstraction reactions of phenanthraquinone with o-substituted toluenes under the irradiation of light. The relative intensities of these signals could be predicted only by the general treatment of the CKO theory, taking account of the electronic singlettriplet interactions (S–T0 and S–T1) of the radical pair. The scalar electronic-coupling constants, Je, were evaluated approximately by comparing the theory with the experimental results and were found to be in the order of 7×109 sec−1. The rather large value of Je was discussed in relation to the nature of the reaction system; consequently, the existance of electronic π–π interaction was suggested for the radical-pair intermediate of the reaction.
Ambident Ion. VI. Kinetical and Thermodynamical Control in the Acylation of β-Dicarbonyl Compounds. Acetylation of Benzoylacetone and Benzoylacetonate Anion
Authors: Suama Masakazu , Nakao Yukimichi , Ichikawa Katsuhiko
Published: July 2006

Kinetically as well as thermodynamically controlled steps have been established in acetylation of ambident ion. Acetylation of sodium benzoylacetonate in pyridine gave initially the kinetically controlled product (I) which isomerized gradually to the thermodynamically controlled (II). C-Acetylation product (III) was formed by the reaction of benzoylacetonate ion with O-acetylbenzoylacetones at higher temperatures. Comparison of the results in the acetylation of benzoylacetone with those of its sodium salt suggested that enolate anion was the reacting species in both processes of O- and C-acetylation. Isomerization between I and II was suppressed in α-picoline or 2,6-lutidine solution. Utilizing these results we have prepared three kinds of acetylated products I, II, and III readily in high selectivity.
Studies of Thioiminocarbonates. I. The Formation and Decomposition of O-Alkyl S-Aryl Thioiminocarbonates in the Reaction of Aryl Thiocyanates with Alcohols in the Presence of the Cyanide Ion
Authors: Tanaka Kazuhiko , Hayami Jun-ichi , Kaji Aritsune
Published: July 2006

The reactions of aryl thiocyanates (I) with alcohol in the presence of cyanide ion were found to give alkyl aryl sulfides (III). The intermediate was isolated in the case of p-tolyl thiocyanate with methanol at 0°C and was determined to be O-methyl S-p-tolyl thioiminocarbonate (IIa) on the basis of NMR and IR spectral studies. The treatment of IIa with the cyanide ion afforded methyl p-tolyl sulfide (IIIa) in a high yield. When a mixture of an equimolecular amount of O-methyl S-p-tolyl thioiminocarbonate (IIa) and O-ethyl S-p-chlorophenyl thioiminocarbonate (IId) was treated with sodium cyanide in ethanol, all the anticipated sulfides—methyl p-tolyl sulfide (IIIa), p-tolyl sulfide (IIIb), methyl p-chlorophenyl sulfide (IIIc) and ethyl p-chlorophenyl sulfide (IIId)-—were isolated. The mechanistic route, which involves the addition of alcohol to aryl thiocyanate, and the dissociation of the resulting O-alkyl S-aryl thioiminocarbonate (II) into aryl mercaptide ion and aryl cyanate, was proposed.
Synthesis and Conformational Studies of [7](2,6)Pyridinophanes
Authors: Fujita Shinsaku , Nozaki Hitosi
Published: July 2006

[7](2,6)Pyridinophane (V) and the 4-deuterio derivative (VD) are prepared from cyclododecane-1,5-diones (IV and IVD). Lithiation at the α-position of V and the subsequent derivation give 1-methoxycarbonyl- (VIII), 1-hydroxy- (IX), 1-oxo- (X), and 1,1-dimethoxy[7](2,6)pyridinophane (XI). A bathochromic shift in UV spectra is observed and ascribed to the nonplanarity of the pyridine ring. The protons on the C4 of these heterophanes experience strong shielding due to the magnetic anisotropy of the respective pyridine rings. The shielding of the C4 protons is more pronounced at low temperatures; this can be explained by assuming an extreme conformation such as XII. The temperature dependence of the NMR spectra is examined, and the energy barriers (ΔGc\eweq) for the conformational changes (XII\ightleftarrowsXII′) are estimated to be 9.0 for V and 9.6 kcal/mol for XI. [7](2,6)Pyrylophanium perchlorate (VI) is prepared, in which a similar shielding effect of the pyrylium ring is observed.
Near Ultraviolet Absorption Spectrum of Pyridine-d5 Vapor
Authors: Hasegawa Yoshinori
Published: July 2006

The near ultraviolet absorption spectrum of pyridine-d5 vapor due to n–π* transition was measured and analyzed. The origin is at 34951 cm−1 and higher than that of pyridine-h5 by 182 cm−1. The ground-state frequencies 582 and 1019 cm−1 and their counterparts of 511 and 953 cm−1 in the upper state dominate the progressions in the spectrum. Besides the above frequencies, several active frequencies were obtained.
Kinetic Studies of the Solvent Extraction of Metal Complexes. I. The Extraction of the Beryllium(II)-TTA Chelate from Aqueous Perchlorate Media into Carbon Tetrachloride and Methyl Isobutyl Ketone
Authors: Sekine Tatsuya , Koike Yasuaki , Komatsu Y\={u}
Published: July 2006

The rate of extraction of beryllium ions from aqueous 4.0m or 0.1m sodium perchlorate-chloride or -nitrate ionic media into carbon tetrachloride or MIBK (methyl isobutyl keton) as a chelate complex with TTA (thenoyltrifluoroacetone) has been determined at 25°C. The rate of extraction in the carbon tetrachloride system is first-order with respect both to the beryllium ion and the dissociated TTA anion in the aqueous phase. The rate constant for this reaction is about 2×104m2min−1. The rates in these systems are not influenced by the replacement of perchlorate ions by nitrate or chloride ions in the ionic media when the ionic concentration is kept constant. On the other hand, it was found that three extraction reactions take place in the MIBK systems. The rate of these extractions is in all cases first-order with respect both to the beryllium ion and the dissociated TTA anion, but is zeroth-, first, or second-order with respect to the perchlorate ions in the aqueous phase. Because of this, the extraction is much faster when the perchlorate concentration is larger; for example, when the concentration of the TTA anion is kept constant, the extraction from a 4.0m sodium perchlorate solution is about 200 times faster than that from the 4.0m sodium chloride solution. From these experimental results, the following conclusions were reached. In the carbon tetrachloride system, the beryllium ion first forms the TTA chelate in the aqueous phase, and then the complex is extracted into the organic phase. The rate-determining step is the 1: 1 complex formation in the aqueous phase. In the MIBK system, on the other hand, the formation of the TTA complex in the aqueous phase, followed by its extraction into the organic phase (zeroth-order reaction with respect to the perchlorate ion), also occurs, but at the same time, the beryllium ion in the aqueous phase is first extracted into the organic phase as ion-pairs, such as BeCl(ClO4) or BeNO3(ClO4) and Be(ClO4)2 (first- and second-order reactions with respect to the perchlorate ions respectively), and the ion-pairs then react with the TTA anions in the organic phase. The enhancement of the rate of extraction by the perchlorate ions in the MIBK system seems to be explained by the overall effect of these extraction mechanisms.
Electron Spin Resonance Study of Short-Lived Free Radicals in Photoreduction of Benzophenone
Authors: Yoshida Hiroshi , Warashina Tetsuo
Published: July 2006

By observing electron spin resonance spectra during photolysis at room temperature, kinetic behaviors of short-lived free radicals are studied in photoreduction of benzophenone in alcohols, especially in ethanol, with and without sodium methoxide. In neutral solution, diphenylhydroxymethyl radicals and hydroxyethyl radicals are observed simultaneously. This is a firm evidence, obtained from ESR, of hydrogen abstraction of excited benzophenone from ethanol. Results indicate that (1) free radicals are the most efficiently generated by the light of ∼350 nm, (2) hydroxyethyl radicals transform into diphenylhydroxymethyl radicals if the concentration of benzophenone is high, and (3) the latter radicals disappear following the second order reaction. In the presence of sodium methoxide, diphenylhydroxymethyl radicals transform into benzophenone ketyl anions.

Rate constants are determined, being 3×107 and ∼104 mole−1·1·sec−1 for the combination reaction between diphenylhydroxymethyl radicals and the proton transfer reaction from diphenylhydroxymethyl radical to methoxide ion, respectively.
Thermoelectric Powers of Molten I2+Te Solutions
Authors: Ichikawa Kazuhiko , Shimoji Mitsuo
Published: July 2006

The initial and steady-state potentials of thermocells of the liquid I2+Te system were measured at temperatures 250–600°C. Cells with a vapor path were used, together with those in which a vapor transport was forbidden. The difference due to these types of cells was found in the values of not the initial thermoelectric powers but the steady-state ones for only solutions with low Te compositions. In the I2-rich region, the mechanism is discussed by using the model of charge-transfer due to I3− as in the case of conductivities and absorption spectra. The thermoelectric data in both the Te-rich and intermediate composition regions suggest that electronic contributions are highly predominant and a transition to delocalized states continuously appears with increasing Te concentration. Some experiments were carried out in order to examine the formation of concentration gradient due to the thermal effect in low Te compositions.
Properties of Water in Macromoleular Gels. III. Dilatometric Studies of the Properties of Water in Macromolecular Gels
Authors: Aizawa Masuo , Suzuki Shuichi
Published: July 2006

The dilatometric properties of W1 W2, and W3, which were proposed by the present authors, for the classification of water in macromolecular gels, are studied over the range from −30 to 60°C. From the results of the thermal expansion of agarose gels and Sephadex (cross-linked dextrans), higher water contents of gel were found to show an extremely sharp volume change at 0°C; on the contrary, lower water contents of gel exhibited no anomalous change in the specific volume in the range from −30 to 0°C, and a gradual decrease in the specific volume was detected with an increase in the temperature in the range from −20 to 0°C for medium water contents of the gel, though the gel was expected to increase in its volume in that temperature range. Thus, the new classification for the states of water in macromolecular gels was shown to be reasonable, at the same time, the transition temperatures of W1 W2, and W3 were evaluated on the basis of the above results.

The thermal expansion of water in macromolecular gels, even of W1 was found to be extremely depressed by the polymers of such gels.
Scmielassical Calculation of the Vibrational Transition Probabilities of Diatomic Molecules in Collision. The Effect of Vibrational Anharmonicity
Authors: Yonezawa Yoshiro , Fueno Takayuki
Published: July 2006

The multi-state semiclassical method proposed by Sharp and Rapp for calculating the vibrational transition probabilities of harmonic oscillators in collision was extended to Morse oscillators. Model calculations have been carried out for the excitation of a vibrational ground-state hydrogen molecule colliding with a helium atom at varying relative velocity. It has been shown that the Morse oscillator model gives greater transition probabilities than the corresponding harmonic oscillator model.
The Crystal and Molecular Structure of Bis(o-ethoxyphenyl)butadiyne
Authors: Taga Tooru , Masaki Norio , Osaki Kenji , Watanabé Tokunosuke
Published: July 2006

The crystal structure of bis(o-ethoxyphenyl)butadiyne has been determined by the statistical method of X-ray analysis. The space group is P21⁄a with two molecules in the unit cell of dimensions a=14.64, b=11.27, c=5.19 Å, and β=105.6°. The crystal structure is built up from columns of the molecules packed along the c-axis. The molecule has a center of symmetry and is almost planar. The diacetylene group is slightly twisted and the three conjugated bond distances of the diacetylene group are 1.434, 1.201, and 1.371 Å.
Effects of External Pressure on the Light Absorption and Fluorescence of s-Tetracyanobenzene Complexes
Authors: Torihashi Yoshikazu , Furutani Yoshifumi , Yagii Kiyoshi , Mataga Noboru , Sawaoka Akira
Published: July 2006

The effects of high pressure on the charge-transfer (CT) absorption and fluorescence spectra of tetracyanobenzene (TCNB) complexes at room temperature have been examined. The pressure-induced change in the absorption intensity indicated the reduction of the distance between donor and acceptor in the complex and the increase in the overlap between their electron clouds. The pressure-induced red shifts of the absorption and fluorescence spectra were almost equal to each other in the case of the TCNB-toluene system, but the former shift was larger than the latter shift in the case of the TCNB-mesitylene system. These results were interpreted in terms of the reduction of the donor-acceptor distance in the complex as well as in terms of electrical solute-solvent interactions. It has been confirmed that the fluorescence quantum yield and the decay time of the complex decrease with the increase in the pressure, and that the rate of the decrease of the former is much larger than that of the latter, in the case of TCNB-toluene system. These results have been interpreted as being due to the pressure-induced increase in the quenching process at the Franck-Condon excited state as well as in the course of the relaxation process from the excited Franck-Condon state to the equilibrium fluorescent state.
Kinetics of Silver(I) Ion Catalysed Oxidation of Glycine by Peroxodisulphate Ion
Authors: Chandra G , Srivastava S N
Published: July 2006

The kinetics of Ag(I) ion catalysed oxidation of glycine by peroxodisulphate in aqueous medium has been studied. The reaction is found to be first order in peroxodisulphate and Ag(I) ions and almost independent of glycine concentration. The rate constant is found to decrease with the increase in the concentration of peroxodisulphate ion. Addition of neutral salts shows a retarding effect. A suitable mechanism has been proposed and a theoretical rate law has been derived to account for the results.
The Dehydrogenation of Butyl Alcohols by the Molten-metal Catalysts
Authors: Kashiwadate Ken , Saito Yasuo , Miyamoto Akira , Ogino Yoshisada
Published: July 2006

In order to investigate the catalytic activity of molten metals, the dehydrogenation reactions of n-butyl alcohol, iso-butyl alcohol, and sec-butyl alcohol were carried out in the presence of molten zinc and molten indium (molten gallium was also used for the dehydrogenation of iso-butyl alcohol). According to the experimental results, all of these molten metals showed persistent catalytic activities and high selectivities for all the test reactions, and the decreasing order of the reactivity of the butyl alcohol isomers was found to be sec-butyl alcohol > iso-butyl alcohol > n-butyl alcohol. Among the three molten metals, i.e. Zn, Ga, and In, the activity and the selectivity of the molten zinc catalyst was outstandingly high. Further, kinetic analyses of the data showed that a compensation effect exists between the apparent activaiton energy, Ea, and the logarithmic frequency factor, logA.
Vibrational Spectra and Normal Coordinate Calculations of HgNH2Cl and HgNH2Br
Authors: Niwa Kiyoshi , Takahashi Hiroaki , Higasi Keniti , Kajiura Teruo
Published: July 2006

Infrared spectra of HgNH2Cl and HgNH2Br and the Raman spectrum of HgNH2Cl have been measured in the region from 4000 cm−1 to 30 cm−1. Effects of changing the X(X=Cl,Br) ion were observed mainly in N–H stretching bands and in lattice vibrations. Calculations of normal frequencies were carried out using a force field which includes inter-molecular forces. An assignment of the lattice vibrations was proposed and the force constants were also calculated. The force constants of the inter-molecular hydrogen bonds N–H···Cl and N–H···Br were obtained as 0.212 mdyn/Å and 0.142 mdyn/Å, respectively.
The Extraction of the Cesium Ion with Some Nitrophenols into Nitrobenzene. II. Homoconjugation Studies by Means of Conductivity Measurements
Authors: Tochiyama Osamu , Koyama Mutsuo , Fujinaga Taitiro
Published: July 2006

In connection with the liquid-liquid extraction study of alkali metal nitrophenolates, ionic equilibria taking place in the systems were studied by means of conductivity and solubility measurements. It was revealed that the adduct formation of p- and m-nitrophenolates consisted of homoconjugation, that is, free nitrophenols are attached not to cations, but to the nitrophenolate anions, thus forming the larger anions and being stabilized in the organic phase. Homoconjugation constants of the nitrophenolates, which are independent of the cations present, were measured. The difference in extraction behaviors was interpreted in terms of the solubilities in both aqueous and organic phases and in terms of the homoconjugation constants.
Anomalous Gas Chromatogram Due to the Oxidation of Porous Polymer Beads by a Sample Containing Oxygen Gas
Authors: Soda Reisuke
Published: July 2006

By the gas-chromatographic analysis of the organic vapor in the air by means of a Porapak column, a broad peak accompanied by long tailing was observed at column temperatures above a certain value with a flameionization or an electron-capture detector. The cause of that peak was investigated using various gases and columns by changing the column temperature. The conclusion was that oxygen in air reacted with polymer beads even at temperatures lower than that cited in the catalogue as temerature to be employed, and the reaction products gave the anomalous broad peaks. The reaction was considered to consist of the oxygenation of polymer beads to produce carbon monoxide, carbon dioxide, formic acid, and the other organic compounds. For Porapak Q and P, the maximum temperature which can be used in safety may be 120°C for an analysis of a sample which consists in greater part of air.
Hot-atom Chemistry of Cobalt-60 Atoms in Neutron Irradiated Organic Solutions of Tris(acetylacetonato)cobalt(III)
Authors: Tominaga Takeshi , Sakai Takuhiko , Fujiwara Kitao
Published: July 2006

Thermal neutron irradiation has been carried out on the solutions of tris(acetylacetonato) cobalt(III) in benzene, ethanol, acetone and acetic acid containing various additives such as metallic salts and mineral acids. The 60Co retention in the irradiated solutions has been found to decrease sharply with the increase in the concentration of various metallic salts. This indicates that the thermal diffusive reactions which contribute greatly to the apparent retention in the irradiated solutions can be suppressed by the addition of adequate metallic salts as scavengers. Salts of the metals which can form more stable complexes with acetylacetone (i.e., Fe(III), Cu(II), Al(III), etc.) work as more effective scavengers in these systems. The upper limit for the primary retention of tris(acetylacetonato)cobalt(III) in the benzene solutions has been estimated as 0.00±0.02%. The use of adequate scavengers appears to be a useful technique to determine the primary retention in the irradiated solution systems. The 60Co retention of the solid complex irradiated at dry ice temperature was 1.4–1.5% irrespective of the organic solvents used for dissolution if they contain ferric chloride, while it increased to 2.0% in the absence of the scavenger.
Kinetics of the Reaction of Americium(III) with Peroxydisulfate
Authors: Ohyoshi Akira , Jyo Akinori , Shinohara Tetsuo
Published: July 2006

Kinetic studies of the americium(III) oxidation have been made in aqueous solutions. The reaction rates are dependent on the concentrations of hydrogen, peroxydisulfate and the silver ion as catalyzers, and on the reaction temperature. The period of induction observed in the initial stage of reaction varies with the concentration of the reactant and with the reaction temperature. The data follow this rate expression:

−\fracd[Am(III)]dt=Kh(k1+k2[Ag+])[S2O82−][Am(III)]·1⁄[H+]

where Kh is the dissociation constant of hydrogen peroxydisulfate, and where k1 and k2 refer to the silver-ion uncatalyzed and catalyzed paths respectively. The energies of activation were determined to be 28.6 kcal/mol for k1 and 17.4 kcal/mol for k2.
A Study of the Catalytic Partial Oxidation of Hydrocarbons. XI. The Catalytic Activity of the MoO3–P2O5 and the MoO3–Bi2O3–P2O5 in the Selective Oxidation of Butene, Butadiene, and Furan
Authors: Ai Mamoru , Suzuki Sadao
Published: July 2006

In the present work, the vapor-phase partial oxidation of cis-2-butene, butadiene, furan, and maleic anhydride was carried out over MoO3–P2O5 (1 : 0.2 atomic ratio) and MoO3–Bi2O3–P2O5 (1 : 1 : 0.2) with a contact time of 1.6 sec, at a concentration of 0.6–1.0%, and in air, in order to elucidate the difference between the two catalysts in their catalytic specificity for the oxidation of these reactants to maleic anhydride. Over the MoO3–P2O5 catalyst, the selectivities of butene, butadiene, and furan to maleic anhydride were 13, 50, and 78% respectively. Over the MoO3–Bi2O3–P2O5 catalyst, the formation of maleic anhydride from the reactants was very small, that of CO2 was important, and the rate of maleic anhydride destruction was fairly high. It is considered that the MoO3–Bi2O3–P2O5 catalyst has almost the same catalytic specificity as the MoO3–P2O5 in the C4H8→C4H2O3 step, but that its activity for maleic anhydride destruction is so high that maleic anhydride cannot be accumulated.
The Effects of Solvents and Acid Catalysts on the Rearrangement of 2-Benzylidenecyclohexanone Oxide
Authors: Hinoue Kenichi , Nojima Masatomo , Tokura Niichiro
Published: July 2006

The rearrangement of 2-benzylidenecyclohexanone oxide (I) to 2-phenylcycloheptane-1,3-dione (II) was carried out in the presence of a Lewis acid or a Brφnsted acid in various media-liquid sulfur dioxide, benzene, and ether. The only reaction product of I with a Brφnsted acid in these solvents was the rearranged compound, II. In addition to II, 2-(α-halobenzyl)-2-hydroxycyclohexanone, (III) or (IV), was also obtained in the reaction of I with a Lewis acid in solutions. Drastic solvent effects were observed on the rate and the distribution of products in this reaction; however, no solvent effect was observed when a Brφnsted acid, which could donate a proton to I, was used as the catalyst. From the variations in the concentrations of the reactant, the intermediate, and the product during the reaction course, the solvent effects upon the reaction pathways were discussed.
Free-Radical Chlorination of Alkylsilanes. VI. The Hydrogen Abstraction from α-Substituted Hydrosilanes by Chlorinated Methyl Radicals
Authors: Nagai Yoichiro , Matsumoto Hideyuki , Hayashi Masaki , Tajima Eiji , Watanabe Hamao
Published: July 2006

Relative rates of hydrogen abstraction from Si-H bonds of α-substituted hydrosilanes by the trichloromethyl or the dichloromethyl radical were determined by allowing the hydrosilanes to compete in pairs for a chlorocarbon compound, carbon tetrachloride or chloroform, at 80°C in the presence of benzoyl peroxide. Results show that relative rates of the investigated hydrosilanes toward the trichloromethyl and the dichloromethyl radicals are satisfactorily correlated with the summation of Taft σ values for the substituent on the central silicon atom, giving ρ values of −0.11 and −0.08, respectively. Linear correlations are also found to exist between the relative rates and the 29Si-H coupling constants.
The Constituents of Hops. VI Studies of the Volatile Composition of Humulus lupulus L. during Ripening
Authors: Naya Yoko , Kotake Munio
Published: July 2006

Evidence is presented for the volatile constituents of hops, not only in the resin glands, the so-called lupulin, but also in the stalk with leaves and in the three crops of cones during ripening. Lupulin shows a specific accumulation of myrcene, and the amount of the volatile constituents increases from fifty times to eight hundred times that in any other part of the plant in the course of ripening. While ripe cones contain neither any germacratrienes, the precursors of several sesquiterpenes, nor any aliphatic aldehydes, the stalk with leaves and the young cones have quite high concentrations of them respectively. Observation suggests that some of the volatile constituents are formed a t an early stage of growth, whilst others are formed later.
Carboxylation of Phenol Derivatives. XX. Syntheses of Phenolpolycarboxylic Acids by the Carboxylation of Alkali Phenoxide in the Presence of Alkali Alkyl Carbonate
Authors: Kito Taketoshi , Hirao Ichiro
Published: July 2006

Phenolpolycarboxylic acids, especially hydroxytrimesic acid, were obtained in good yields by heating alkali phenoxide under a carbon dioxide pressure in the presence of alkali alkyl carbonate. Hydroxytrimesic acid was obtained in the best yield by the reaction of potassium phenoxide and potassium alkyl carbonate. In this reaction, neither a superatmospheric pressure nor a high reaction temperature was needed. The formation processes of phenolcarboxylic acids are also discussed.
The Copolymerization of 2-Chloroacrylaldehyde with Styrene
Authors: Matsubara Yoshio , Kavi Parimal R , Yoshihara Masakuni , Maeshima Toshihisa
Published: July 2006

The copolymerization of α-chloroacrolein (M1) with styrene (M2) has been investigated. An alternating copolymer was obtained without an initiator in dimethyl sulfoxide at 60°C. The formation of a charge-transfer complex between the respective monomers was observed by the continuous-variation method, and it was found that this complex plays an important role in the polymerization. Meanwhile, in the case of the BF3OEt2-catalyzed system, it was observed that the polymerization temperature strongly affected the copolymerizability and the structure of the copolymer.
Syntheses of N-Substituted Carbamimidoylformic Acids
Authors: Yoshimura Juji , Fujimori Kunihiko , Sugiyama Yuichi , Ando Hiroaki
Published: July 2006

A few synthetic methods of N-substituted-carbamimidoylformic acid (6) were examined. Among them, condensation of ethyl 1-carbethoxyformimidate or ethyl thiooxamidate with amines and followed by partial hydrolysis gave unsuccessful results, except of the case of benzylamine in the latter reaction. Direct substitution of potassium thiooxamidate (9) with alkylamines in water gave 6, potassium and/or alkylammonium N-substitutedthiooxamidate in fairly good yield, depending on conditions used. The presence of heavy metal ions in the reaction system caused an extensive decomposition of 9, however, the substitution proceeded smoothly by treatment of alkyl- and aryl-ammonium N-unsubstituted- or N-substituted-thiooxamidate in methanol with mercuric oxide or lead oxide to give in a good yield 6 or N,N-disubstituted-carbamimidoylformic acid, respectively.
Adsorptive Properties of Decationated Zeolite for Some Aromatic Hydrocarbons as Observed by Gas Chromatography
Authors: Matsumoto Hiroshige , Futami Hideo , Kato Fumiyoshi , Morita Yoshiro
Published: July 2006

The adsorptive properties of decationated zeolite for simple aromatic hydrocarbons, such as benzene, toluene, ethylbenzene, and xylenes were investigated by means of gas chromatography at 270–330°C. The specific retention volumes of these alkylbenzenes increased with the increase in the sodium ion content and the rise in the pretreatment temperature of zeolite. The adsorption heat was substantially independent of the sodium content, but slightly increased with the rise in pretreatment temperature above 550°C. A linear relationship was found between the decrease in the ionization potential of aromatic hydrocarbons and the increase in the heat of adsorption. For comparison, the adsorption of ethylene was also examined. With the rise of pre treatment temperature of zeolite, the retention volume of ethylene decreased. On introduction of water to the system, the retention volume of ethylene reversibly increased, whereas that of aromatic hydrocarbons decreased. In accordance with the decationation process of zeolite proposed by Hall et al., these aromatic hydrocarbons are adsorbed preferably on tricoordinated aluminum site as well as on sodium ion to form the charge transfer complex, while ethylene interacts with hydroxyl group to form the carbonium ion or hydrogen-bonded complex.
Dielectric Relaxation of 1,2-Dichloroethane and 1,2-Dibromoethane in the Liquid State
Authors: Hasan Abul , Pal Arati , Ghatak Alpana
Published: July 2006

The activation energies for dielectric relaxation (ΔHτ) of the gauche rotational isomers of 1,2-dichloroethane and 1,2-dibromoethane in the liquid state have been determined from the dielectric relaxation data obtained from the absorption in 1.62 cm and 3.20 cm microwave regions at different temperatures. The activation energies (ΔHτ) in both the liquids obtained in the present investigation agree fairly well with the values of electrostatic self energy of the polar isomers in the liquid state calculated theoretically by Wada.
Ultrasonic Study on Aqueous Solutions of Amino Acids
Authors: Sasaki Katsutaka , Arakawa Kiyoshi
Published: July 2006

Ultrasonic experiments for aqueous solutions of amino acids (glycine, l-alanine, l-valine, and l-leucine) were carried out by means of pulse technique in order to study the nature of solute-solvent interactions. The sound velocity and absorption coefficient were determined for aqueous solutions in the frequency range 15–45 MHz, at temperatures 10–30°C. No relaxation frequency was observed in all the solutions. The absorption coefficient for glycine solutions at low concentrations is nearly equal to that for pure water. The result is consistent with the idea that glycine molecules behave as a structure breaker within water. Concerning the concentration dependency of sound velocity and absorption, no appreciable difference is observed in various solutions of amino acids in spite of difference in the size of hydrocarbon side chains in solute molecules. It is concluded that the behavior of l-alanine and its higher homologues in water dose not differ from that of glycine.