bluuebunny/crossref_metadata_2025 huggingface dataset:
Continuous Determination of Nitric Oxide and Nitrogen Dioxide in the Atmosphere
Authors: Yanagisawa Saburo , Yamate Noboru , Mitsuzawa Shumpo , Mori Masaki
Published: July 2006

Continuous determinations of nitric oxide and nitrogen dioxide in the atmospheric air by the use of a modified Saltzman reagent will be described. Measurement was made intermittently, once every 30 min., by an automatic continuous analyzer equipped with a single-path colorimeter. The response of the analyzer was obtained as an average of the concentration of nitrogen oxides over a period of 25 min. Two bubblers were used for absorbing nitrogen oxides into the modified Saltzman reagent, whose transmittance was measured for the determination. One bubbler was designed to absorb nitrogen dioxide, and the other, nitric oxide plus nitrogen dioxide after the oxidation of the nitric oxide by permanganate. The oxidizing efficiency of the permanganate was 96–100 per cent. The acetic acid in the Saltzman reagent was replaced with n-propyl alcohol in the modified Saltzman reagent; the spontaneous coloration and corrosive quality of the reagent was decreased by this substitution. The concentration of nitric oxide was obtained from the difference between the two responses of the analyzer, while the concentration of nitrogen dioxide could be read directly from the indication of the recorder. The transmittance ratio method was applied to the measurements, accurate determinations were possible, even at high blank values. Therefore, the reagent was used repeatedly by cycling it on the basis of measuring the difference in the coloration of the reagent before and after the absorption of nitrogen oxides. The analyzer could be used for a long period without changing the reagent.
The Isomers of the Hydrogenation Products of Bisphenol A. The Separations and Configurations of Three Isomers of 2,2-Bis-(4-hydroxycyclohexyl)propane and Two of 2-(4-Hydroxycyclohexyl)-2-(p-hydroxyphenyl)propane
Authors: Terada Akira
Published: July 2006

Hydrogenations of bisphenol A (I) over Raney nickel (W-1) and Urushibara nickel A and B have been carried out, and three stereoisomers of 2,2-bis(4-hydroxycyclohexyl)propane (II) and two of 2-(4-hydroxycyclohexyl)-2-(p-hydroxyphenyl)propane (III) have been isolated from the products. The configurations and the preferred conformations of the II isomers, cis-cis (m. p. 174–175°C), cis-trans (164–165.5°C) and trans-trans (188–189°C), and of the III isomers, cis (159–161°C) and trans (150.5–151.5°C), have been determined by means of the infrared and nuclear magnetic resonance spectra, inversions over sodium to the stable isomers, and other methods. When heated with purified methanol, 2,2-bis(4-ketocyclohexyl)propane prepared from the chromium trioxide oxidation of an isomeric mixture of II afforded 2,2-bis(4,4-dimethoxycyclo-hexyl)propane, m. p. 140.5–141.5°C. The recrystallization of IIIt from benzene yielded IIIt·C6H6. Treating IIIc with acetic anhydride gave 2-(3-cyclohexenyl)-2-(p-hydroxyphenyl)propane (where c: cis and t: trans).
Studies of C-Substituted Tartaric Acid. II. On the Configurations. of Isomeric 2-Methyltartaric Acids, 1,2-Dihydroxycyclohexane-1,2-dicarboxylic Acid and 2, 3-Dimethyltartaric Acids
Authors: Tatsumi Susumu
Published: July 2006

The assignments of the erythro-threo configuration to isomeric 2-methyltartaric acids and the-cis-trans configuration to isomeric 1,2-dihydroxycyclohexane-1,2-dicarboxylic acids were made on the basis of the infrared absorption spectra of their calcium salts. Thus, the isomer of 2-methyltartaric acid, with a m. p. of 146°C, corresponds to the erythro form, and the other isomer, with a m. p. of 161°C, to the threo form; also the one isomer of isomeric 1,2-dihydroxycyclohexane-1,2-dicarboxylic acids with a m. p. of 154°C corresponds to the cis (meso) form, and the other, with a m. p. of 180°C, to the trans (racemic) form. The configurations of the compounds are discussed in comparison with those of tartaric acid and 2,3-dimethyltartaric acid, the latter of which was recently decided by optical resolution by present author (S. Tatsumi, This Bulletin, in press.).
Vinyl Polymerization. CXLVI. The Influence of Dibenzoyl Disulfide Derivatives on Radical Polymerizations
Authors: Tsuda Kazuichi , Otsu Takayuki
Published: July 2006

In order to study the effects of aromatic sulfur derivatives on radical polymerizations, dibenzoyl disulfide (DBDS) and its derivatives were prepared and used as initiators or chain transfer agents for the polymerizations of styrene and methyl methacrylate. All of these derivatives failed to act as initiators of thermal polymerizations, but they did prove effective photosensitizers. The rates of polymerizations were found not to be proportional to the square-root concentration of the initiator (DBDS) used. The sulfur radical derived from the photo-dissociation of DBDS affected not only the initiation reaction, but also the termination reaction. The chain transfer constants to DBDS derivatives in the polymerization of styrene and methyl methacrylate showed no linear relationship with Hammett’s equation (logC⁄C0=ρσ), but a linear relationship was obtained when a modification of Hammett’s equation (logC⁄C0=ρσ+γER) was applied. From the plot obtained by the use of logC⁄C0=ρσ+γER, the γ value, which indicates the extent of resonance stabilization in the transition state was found to be 6.0 upon the polymerization of styrene at 60°C. Under similar conditions, however, the γ-value for benzoyl peroxide was calculated as 3.0 from the results of Cooper. This difference may be explained from an increased 3d-orbital resonance stabilization of DBDS in the transition state.
Studies of Thio Acids. VII. The Synthesis of Thiopalmitic Acid and Thiomyristic Acid
Authors: Hirabayashi Yoshio , Mizuta Masateru , Mazume Tetsuro
Published: July 2006

Thiopalmitic acid, C15H31COSH (m.p. 30.8–31.3°C), and thiomyristic acid, C13H27COSH (m.p. 19.8–20.3°C), were synthesized by the reaction of sodium hydrogen sulfide in ethanol with palmitoyl and myristoyl chlorides respectively. The infrared absorption spectra of thiopalmitic and thiomyristic acids indicate that both acids assumed the thiolic acid form. Dipalmitoyl disulfide (m.p. 76.0–76.5°C) and ethyl palmitate, and dimyristoyl disulfide (m.p. 70.5–71.5°C) and ethyl myristate were isolated as by-products.
Asymmetric Hydrogenation with Modified Raney Nickel. VIII
Authors: Izumi Yoshiharu , Tatsumi Susumu , Imaida Masami
Published: July 2006

Asymmetric hydrogenation catalysts were prepared by modifying Raney nickel with aqueous solutions of d-tartaric acid, monomethyl d-tartrate, l-erythro- and d-threo-2, 3-dihydroxybutyric acid, l-malic acid, (+)-erythro- and (−)-threo-3-methylmalic acid, l-citramalic acid and l-methyl-succinic acid. Their asymmetric activities in the hydrogenation of methyl toacetate to methyl 3-hydroxybutyrate were compared with each other in order to study the effect of the chemical structure of the modifying reagent on the activity. Monomethyl d-tartrate, l-erythro- and d-threo-2, 3-dihydroxybutyric acid are less effective in asymmetric activity than d-tartaric acid. On modification with these three reagents, optimum asymmetric activities were obtained under acidic conditions. With d-tartaric acid, however, while high asymmetric activities were obtained at pH 5–9, there was a considerable decrease in activity at lower pH values. This suggests that the β-carboxyl group of tartaric acid plays an important role in the modification. (−)-threo-3-Methylmalic acid is more effective in asymmetric activity than l-malic acid, while (+)-erythro-3-methylmalic acid and l-citramalic acid are less effective. It has been suggested that these differences are related to hindrances due to the methyl groups on the α- or β-asymmetric centers, and also related to the correlations of the configurations of the asymmetric centers of 3-methylmalic acids. l-Methyl-succinic acid has little asymmetric effect on Raney nickel.
A Spectrophotometric Study of the Complex Formation between Iron(III) and Sulfosalicylic Acid
Authors: Ogawa Kin’ya , Tobe Nobuko
Published: July 2006

A spectrophotometric study of the complex formation between iron(III) and sulfosalicylic acid was carried out over the pH range up to 8; further, an attempt was made to test the applicability of sulfosalicylic acid as a reagent for the spectrophotometric determination of iron(III) in the presence of iron(II). The absorption maxima are found at 510 mμ independently of the pH between 1 to 2.5, while they shift in the direction of shorter wavelength as the pH rises. It was concluded that three complex species, Fe(Su), Fe(Su)23−, and Fe(Su)36−, are formed successively in acid solutions; their stability constants were determined to be:

(Remark: Graphics omitted.)

where Su3− denotes the sulfosalicylate anion, C6H3(O−)(COO−)(SO3−). If the pH of the solution is adjusted from 3 to 4.5 and if the absorbancy measurements are made at 480 to 490 mμ, sulfosalicylic acid can be used as a reagent for determining iron(III) in the presence of iron(II). The optimum concentration of iron(III) is 2 to 10 p. p. m.; iron(II) does not interfere, even at a concentration of 100 p. p. m.
Studies of Organic Catalytic Reactions. IV. A Redox Reaction between Unsaturated Organic Compounds and Primary Alcohols in the Presence of Nickel Catalysts
Authors: Sakai Koji , Ito Takehiko , Watanabe Ken-ichi
Published: July 2006

Styrene, mesityl oxide, benzonitrile and nitrobenzene are reduced when heated with primary alcohols, such as methanol, ethanol, 1-butanol and benzyl alcohol, in the presence of nickel catalysts. On the other hand, aldehydes are obtained by the dehydrogenation of the primary alcohols. The relative reactivity of the functional groups for the reduction is as follows: C=C>C≡N>NO2>C=O. The carbonyl group and the benzene nucleus can not be reduced under these reaction conditions. A selective reduction occurs in the reaction with mesityl oxide. The lower limit of the reaction temperature depends on the combination of the two species of the hydrogen donor (primary alcohol) and the acceptor compounds. The use of a large excess of alcohols for the reduction is effective in this redox reaction. In the reaction between styrene and benzyl alcohol, the ratio of the decreased amount of styrene to the increased amount of ethylbenzene is always 1 : 1, as determined by gas chromatographic analysis.
The Relative Reactivities of Alkyl Acrylates in Their Radical Copolymerizations
Authors: Otsu Takayuki , Ito Toshio , Fukumizu Tomiya , Imoto Minoru
Published: July 2006

In order to clarify the effect of the alkyl groups in alkyl acrylates (RA) on their reactivities to the attack of a radical, the copolymerization of RA (M2) with styrene (M1) has been carried out at 60°C. From the results obtained, the monomer reactivity ratios and the Q2 and e2 values were determined. It was found that the relative reactivities (1/r1) of RA to a polystyryl radical were correlated only by the polar substituent constant (σ*) of the alkyl group in RA, not by their steric substituent constant (Es) in Taft’s equation:

log(1⁄r1)=ρ*σ*+δEs

According to the above equation, the ρ* and δ values were obtained as 0.56 and 0, respectively. It was also observed that the Q2 and e2 values for RA were correlated by Taft’s σ* substituent constant.
Resonance Effect in Hammett Relationship. IV. Linear Free Energy Relationship based on the Normal Substituent Constants
Authors: Yukawa Yasuhide , Tsuno Yuho , Sawada Masami
Published: July 2006

A set of normal substituent constants, σ0, was derived from the rates of alkaline hydrolysis of m- and p-substituted ethyl phenylacetates in 60% (v/v) aqeuous acetone at 25.0°C. The obtained values of σ0-constants were generally identical with Taft’s values within experimental uncertainty. On the basis of the derived σ0, substituent effects on the general electrophilic reactions were correlated excellently by the equation, logk⁄k0=ρ(σ0+rΔ\barσR+) where Δ\barσR+ corresponds to the exaltation of Brown and Okamoto’s σ+ from σ0. The similar treatment could be applied also to the nucleophilic reactions. The utility of this equation for the estimation of resonance contribution and for the consideration of reaction mechanisms are discussed.
Nuclear Magnetic Resonance Studies of the Intermolecular Interaction of Amides and Some Other Related Dipolar Molecules
Authors: Yonezawa Teijiro , Morishima Isao
Published: July 2006

The chemical shifts for N,N-disubstituted amides and some other isoelectronic compounds as pure liquid and in dilute solutions in CCl4 are reported. The characteristic shifts generally observed on going from a CCl4 solution to pure liquid are explained in terms of specific self-association in the pure liquid.
The Vibrational Assignments of Sulfuryl-Fluoride, -Chloride and -Fluorochloride and Their Transferable Force Constants
Authors: Toyuki Hiroshi , Shimizu Kazuhiro
Published: July 2006

A normal coordinate treatment has been carried out on the basis of the Urey-Bradley force field in order to obtain a set of the most probable assignments and the transferable force constants for the sulfuryl fluoride, the chloride and the fluorochloride series. The assignments selected and the force constants obtained have been satisfactory. The potential energy distributions have been calculated and the vibrational modes have been estimated for each molecule.
The Isocyanurates. III. The Formation of Tributyl Isocyanurates from Butyl Bromides in the Presence of 1-Butanol
Authors: Nagasawa Atsuo , Kitano Hisao , Fukui Kenichi
Published: July 2006

The reaction of n-butyl or s-butyl bromide with potassium cyanate in dimethylformamide was carried out at 100°C for 3 hr. to give tri-n-butyl or tri-s-butyl isocyanurate. In this process, the presence of unpolymerized n-butyl or s-butyl isocyanate in the reaction mixture was detected by treating the mixture with benzylamine, thus forming 1-n-butyl or 1-s-butyl-3-benzyl urea. The presence of 1-butanol in the reaction system resulted in an increase in the yield of the corresponding isocyanurates. This tendency was remarkable when s-butyl bromide was used as a starting material. The addition of n-butyl N-n-butyl- or n-butyl N-s-butylcarbamate to the reaction system strongly accelerated the formation of isocyanurates. The acceleration due to the addition of 1-butanol described above was, therefore, attributed to the effect of carbamates formed in the reaction system. An attempt to trimerize n-butyl or s-butyl isocyanate in the presence of carbamates and dimethylthylformamide, or in the presence of carbamates and potassium cyanate, resulted in failure. Therefore, carbamates acted as strong accelerators for the trimerization of butyl isocyanates, in cooperation with basic alkali metal salts, such as potassium cyanate, in dimethylformamide.
Studies of Scandium in Various Solutions. II. The Extraction of Scandium(III) with Tributyl Phosphate from Perchlorate-Chloride and Perchlorate-Nitrate Media
Authors: Sekine Tatsuya , Hamada Takeshi , Sakairi Mitsuo
Published: July 2006

The distribution of scandium(III) between organic tributyl phosphate solutions and aqueous perchlorate, nitrate, chloride solutions or mixed solutions of perchlorate-nitrate, perchlorate-chloride has been determined.

The distribution of scandium between 50% tributyl phosphate - chloroform and 4 m H(Cl, ClO4) or 4 m H(NO3, ClO4) in some chloride or nitrate concentration region was higher than any of that distribution between the organic phase and 4 m perchloric acid, 4 m hydrochloric acid or 4 m nitric acid. It seems that the enhancement of the distribution ratios can be attributed to the extraction of mixed ligand complexes, but no simple relationship has been established between the distribution ratios and the proportion of the complex species in the aqueous phase as calculated from the previous data.
Intramolecular Hydrogen Bonds. VIII. Isomeric Hydroxycyclohexylcarbinols and Bis-hydroxymethyl-cyclohexanes
Authors: Mori Nobuo , Tsuzuki Yojiro
Published: July 2006

The preferential direction of intramolecular hydrogen bonding in isomeric hydroxycyclohexyl-carbinols in dilute carbon tetrachloride solutions has been investigated by infrared spectroscopy. The 1-hydroxy isomer contains a tertiary hydroxyl group predominantly bonded to the oxygen atom of a primary hydroxyl, while the cis- and trans-2-hydroxy isomers contain a primary hydroxyl group mainly bonded to the oxygen atom of a secondary hydroxyl; the other isomers are internally unbonded. On the other hand, bis-hydroxymethyl-cyclohexanes other than the 1,1- and 1,2-isomers are unbonded. These findings can be explained in terms of the acidity of the hydroxyl groups and the steric effect on the orientation of the groups.
The Spectra and the Conductances of Alizarine Saphirol SE in Water-Ethanol Mixtures
Authors: Mitsuishi Masaru , Aida Gensaku
Published: July 2006

In order to explore the behavior of Alizarine Saphirol SE in water-ethanol mixtures, the absorption spectrum and the conductance of the dye solution were obtained. A characteristic spectrum of the dye aggregate in water is found to change gradually into a monomer spectrum with an increase in the proportion of an added ethanol. Moreover, the dye is found to show marked McBain effect in water, while showing a conductance curve typical of a weak electrolyte in 58.7% (v/v) ethanol.
Altenin. II. The Structure of Altenin
Authors: Sugiyama Noboru , Kashima Choji , Hosoi Yoshitaka , Ikeda Tsuneo , Mohri Ryotaro
Published: July 2006

Altenin, a metabolite of Alternaria Kikuchiana Tanaka, produces the black spot disease on the leaves and fruits of the pear. The optimum conditions for a 200-1. tank culture of this fungus will be described. Altenin has been tentatively deduced as being an ethyl ester of a C7-carboxylic acid. Of the four expected tautomeric structures, the probability of a furanose ring structure will be demonstrated. There is only one asymmetric center in altenin, at the position α to the ethoxycarbonyl group; this belongs to the l-lactic acid configuration.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. VI. The Catalytic Mechanism of Boron Trifluoride Coordination Complexes in Ethylene Dichloride
Authors: Miki Tetsuro , Higashimura Toshinobu , Okamura Seizo
Published: July 2006

The initiation mechanism in the cationic polymerization of trioxane by the BF3 coordination complex catalyst was studied in ethylene dichloride at 30°C. The coordination complexes of BF3 with diethyl ether (Et2O), ethyl alcohol (EtOH) and acetic acid (AcOH) were used as catalysts. Under similar conditions, the rates of polymerization decreased in the order: BF3·EtOH>BF3·AcOH>BF3·Et2O, whereas the molecular weights of the polymers decreased in the order: BF3·Et2O>BF3·EtOH\simeqBF3·AcOH. The molecular weight of the polymer formed was unaffected by the addition of the same compound as the donor molecule in the BF3 coordination complex. However, on the addition of EtOH to the polymerization system catalyzed by BF3·Et2O, the rate of polymerization increased and the molecular weight of the polymer decreased. On the other hand, the addition of Et2O to the system catalyzed by BF3·EtOH decreased the rate of polymerization and increased the molecular weight of the polymer formed. The order of catalytic reactivity and the effect of the additive support the idea that the initiation reaction, is not an interaction of the BF3 molecule with trioxane but an addition of the cation produced from the BF3 coordination complex to the trioxane molecule.
Styrene Derivatives. IX. 2-Benzyl-2-phenyl-3-aminomethyl-trimethylene Oxides and Related Compounds
Authors: Terada Akira
Published: July 2006

3-Chloromethyl-4-chloro-1,2-diphenylbutan-2-ol was obtained by a Grignard reaction of 2-benzoyl-1,3-dichloropropane using benzyl chloride, which was turned into 2-benzyl-2-phenyl-3-chloromethyl-trimethylene oxide by the alkali dehydrochlorination. Heating this oxide with an excess of piperidine at 170°C for 22 hr. gave 2-benzyl-2-phenyl-3-piperidinomethyl-trimethylene oxide and a small amount of 1,2-diphenyl-3-piperidinomethyl-2,4-butanediol. The same procedures with morpholine gave 2-benzyl-2-phenyl-3-morpholinomethyl-trimethylene oxide; with ethanolic dimethyl amine, however,afforded only 1,2-diphenyl-3-dimethylamino-methyl-2,4-butanediol.
Pyrazolotropolones and Their Derivatives
Authors: Itô Shô , Takase Kahei , Kawabe Norio , Sugiyama Hiroshi
Published: July 2006

Two new methods have been developed to synthesize pyrazolotropone derivatives. 2-Methoxy-3, 5, 7-tribromotropone reacts with diazomethane to yield 4, 6-dibromo-7-methoxy-1-methyl-8(1H)-cyclohepta[c]pyrazolone, whereas the alkaline treatment of 4-acetyltropolone tosylhydrazone provides 3′-methylpyrazolo[3, 4-c]tropolone and 3′-methylpyrazolo[4, 3-d]tropolone. The structure of these products has been elucidated.
Studies of the Chemiluminescence of Several Xanthene Dyes. I. Kinetic Studies of Uranine and Eosine Chemiluminescence
Authors: Kamiya Isao , Iwaki Ryojirô
Published: July 2006

A kinetic study of the chemiluminescence in alkaline solutions of several xanthene dyes with hydrogen peroxide was carried out in the hope of gaining some insight into the mechanism of the luminescent reaction. When the concentrations of sodium hydroxide and hydrogen peroxide were kept constant, the decay curve of the luminescence was represented by It=Aexp(−at), where It is the light intensity at time t ; a is equal to the rate constant of the decomposition of the dye (first order with respect to the dye concentration) and A is a parameter proportional to the initial dye concentration. The lifetime of the luminescent reaction was prolonged by the addition of such organic solvents as alcohol and dioxane; the a value decreased, while the A value remained unchanged. Both the a value and the A value increased with the elevation of the reaction temperature.
The Photo-ionization of Molecules in Solutions. III. Photo-ionization and Recombination Processes of N,N,N′,N′-Tetramethyl-p-phenylenediamine in Various Organic Solvent
Authors: Yamamoto Naoto , Nakato Yoshihiro , Tsubomura Hiroshi
Published: July 2006

Flash photolysis studies of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) were made in various solvents at room temperature. The transient absorption spectrum of the cation, TMPD+ , was observed in polar solvents. The transient was also observed in a viscous, non-polar solvent. It has a spectrum different from that of TMPD+ . Its absorbance is proportional to the flash-light intensity, and it decays exponentially, with τe=82 μ sec. This absorption is attributed to the triplet-triplet transition of TMPD. With aerated solutions, no transient spectrum was observed. The fluorescence and the phosphorescence of TMPD caused by direct excitation were investigated, together with those induced by the recombination of electrons and TMPD+ in non-polar matrices stimulated either thermally or by infrared light. The absorption spectra of TMPD in a non-polar matrix at a low temperature were investigated by means of the cross-illumination method, and the time dependence of the absorption was followed. The ionization and the recombination processes were then discussed by the use of these results.
A Comparison of the Radiation-Induced Reaction with Photochemical and Thermal Reactions. I. The Radiation-Induced Isomerization of o-Nitrobenzaldehyde in the Solid State
Authors: Sugimori Akira , Nakata K\={o}ichi , Hirai Hachiro
Published: July 2006

The radiation-induced reaction of o-nitrobenzaldehyde in the solid state was investigated. Isomerization to o-nitrosobenzoic acid preferentially took place. This suggests that the γ-ray irradiation produces effectively the excited o-nitrobenzaldehyde which is identical with that produced by ultraviolet irradiation.
Unit Cell Metastable-form Constants of Various Phthalocyanines
Authors: Ashida Michio , Uyeda Natsu , Suito Eiji
Published: July 2006

Thin films of phthalocyanine compounds formed on cleaved surfaces of muscovite by the vacuum-condensation method showed well-defined single-directional orientation when their substrates were preheated at 300°C for one hour and then kept at 150°C. Their electron diffraction patterns were fiber diagrams, the fiber period of which coincided with the unit-cell length of the b-axis of the individual compounds. When the substrates were preheated at 400°C for one hour and then kept at 150°C, the films formed on the muscovite surface were composed of discrete crystals with a different orientation. Electron-diffraction patterns from the films revealed that the b-axis of the crystal was inclined to the substrate surface. The cross-grating patterns of the (h0l) plane were obtained when the inclination of the films was properly adjusted to the incident beam. The unit-cell constants of platinum-phthalocyanine vacuum-condensed on muscovite were revealed to be as follows with the monoclinic space group C2⁄c: a=23.18 Å, b=3.818 Å, c=23.84 Å, and β=91.9 °. Films of Cu-, Co-, Fe-, Ni- and metal-free phthalocyanines exhibited an orientation similar to that of the platinum derivative. High-resolution electron-diffraction patterns revealed that all the compounds assumed a conspicuous isomorphism with one another and occurred in the metastable forms of their dimorphs.
The Orientation Overgrowth of Metal-phthalocyanines on the Surface of Single Crystals. I. Vacuum-condensed Films on Muscovite
Authors: Ashida Michio
Published: July 2006

When substrate muscovite is preliminarily heated at 300°C for one hour and then kept at 150°C to 200°C during deposition in vacuo, Cu-phthalocyanine films condensed on it show parallel b-axis orientations, including single- and triple-directional orientations. The b-axis of the crystal runs parallel to the substrate face. On the other hand, when the substrate is preliminarily heated at 400°C and then kept at 150°C, films vacuum-condensed on it occur in a standing b-axis orientation. The high-resolution electron-diffraction pattern of the film reveals that the a-, b- and c-axes of the crystal are inclined to the normal of the substrate face at angles of about 75°, 32° and 118° respectively. An electron micrograph of the film shows that as discrete crystals grow they orient themselves in either of two different directions. The crystal which assumes the standing b-axis orientation has its (31\bar3) plane almost parallel to the substrate face. Pt-phthalocyanine film also assumes the standing b-axis orientation, in which the a-, b- and c-axes of the crystal are inclined to the normal of the substrate face at angles of about 74°, 35° and 120° respectively. It turns out that the molecular plane comes in contact with the muscovite surface in the case of the standing b-axis orientation. A plausible explanation of the origin of these orientations is presented in terms of the dehyroxylation of the surface mica layer caused by the thermal treatment.
The Mechanism of the Catalytic Hydrogenation of Propene on Nickel, Palladium, and Platinum (The Application of Microwave Spectroscopy to Isotopic Analysis)
Authors: Hirota Kozo , Hironaka Yoshie
Published: July 2006

The catalytic hydrogenation of propene with deuterium gas and its isotopic exchange reaction with deuterium oxide have been carried out at room temperature, and the remaining propene has been subjected to microwave spectroscopic analysis so as to determine the isotopic isomer-distribution of propene-d1 and -d2. From the results, the following conclusions have been drawn: (1) the rate-determining step in the hydrogenation on platinum as well as nickel and palladium catalysts is the addition of hydrogen to the half-hydrogenated species; (2) the kinds of chemisorbed species and their distribution prior to the rate-determining step are not always the same, but depend on the metals, and (3) the life-time of the chemisorbed propene is shorter than the successive time interval of its exchange process on nickel, but this is not the case on platinum nor, probably, on palladium.
Studies of the Chemiluminescence of Several Xanthene Dyes. II. The Chemiluminescence Emission Spectra of Uranine and Eosine
Authors: Kamiya Isao , Iwaki Ryojirô
Published: July 2006

The emission spectra of uranine and esoine chemiluminescence with hydrogen peroxide were measured photoelectrically and were compared with the fluorescence spectra of the dyes. The apparent spectra did not give the true energy distribution of the emitted light, because self-absorption took place. When the dyes were oxidized with ozonized air, the apparent emission spectra were very similar to those obtained when the dyes were oxidized with hydrogen peroxide. This would indicate that the emitting species are the same in the two reaction systems. The emission from the dye-ozone reaction was intense, and the spectrum could be compared with the fluorescence spectrum by employing a system with a low dye concentration. The coincidence of the two spectra was clearly demonstrated. The chemiluminescence spectrum of uranine at a high dye concentration in the presence of hydrogen peroxide was compared to the “chemi-fluorescence” spectrum of the luminol-dye system. The two systems gave almost the same spectrum. It may be concluded that the emissions from uranine and eosine chemiluminescence are the fluorescence emissions of the dyes and that the emitting species are the excited singlet states of uranine and eosine.
On the Preparation of Cadmium Sulfoselenide by the Wet Processes
Authors: Hashimoto Kosiro , Yamaguchi Goro , Toda Yoshitomo
Published: July 2006

The super-homogeneous coprecipitation method, in which the binary solution reactants made to mix and react in a moment, thus reducing a super-homogeneous precipitate, has been used recently in the preparation of catalysts. The coloring temperature of the cadmium sulfoselenide red pigment can be lowered to 350°C by this method, while, when the usual wet method is used, the temperature is between 450 and 650°C. This is because a very homogenous solid solution can be formed by the super-homogeneous coprecipitation method. This method is also effective in making an anionic solid solution of A(X, Y) with different anions of X and Y. Spectral reflectance measurements and X-ray analysis in the present work have shown that the coloring temperature has been considerably lowered and the transformation of the β-Cd(Se, S) into the a form has been accelerated by the method.
Studies of Some Telluro-Vanadomolybdates
Authors: Prasad Sarju , Pathak K C
Published: July 2006

Ammonium telluro-vanadomolybdate, 6(NH4)2·TeO3·3V2O5·4MoO3·15H2O, has been synthesized, its properties studied, and its composition determined by analytical methods. Copper, silver, calcium, strontium, barium and lead salts have then been prepared from the ammonium salt. D. T. A. of ammonium and strontium salts have been carried out to investigate the thermal changes. The infrared spectra of the ammonium salt and its dehydrated product have been recorded, and the characteristic frequencies assigned.
Electrode Processes Followed by Chemical Reactions Involving Electroactive Species. II. A Study on the Substitution Reaction Involving Chromium(II)
Authors: Ogino (née Ebata) Kazuko , Tanaka Nobuyuki
Published: July 2006

The one-electron reduction wave of hexamminechromiuni(III) ions at the dropping mercury electrode splits into two steps by the presence of manganese (II) and ethylenediaminetetraacetato-manganate(II) (MnY2−; Y4− represents a quadrivalent ethylenediaminetetraacetate anion) ions. The limiting current of the first step was considered to depend on the rate of the formation of CrY2− by the substitution reaction of MnY2− and chromium(II) ions which were produced at the electrode by the reduction of the chromium(III) complex ions. From the change in the limiting current of the first step by the change of the concentrations of Mn2+, MnY2− and H+ the rate constants of the complex-forming reaction

(Remark: Graphics omitted.)

were obtained to be K1f=8×107 l.mol−1sec−1,K1b=4×104 l.mol−1sec−1 (ionicstrength 1.0, 25°C)
The Radioactivation Analysis of Semiconductor Graphite for Nitrogen by the 14N(p, α)11C Reaction
Authors: Nozaki Tadashi , Okuo Takayasu , Akutsu Hiroyuki , Furukawa Michiaki
Published: July 2006

The excitation curve for the 14N(p, α)11C reaction was measured up to a proton energy of 15 MeV.; the reaction was found to have a fairly high cross section for a sensitive determination of nitrogen by radioactivation. A convenient technique was developed for the rapid quantitative conversion of the irradiated graphite into carbonate within a closed system. This technique makes possible the determination of a trace (down to several p.p.b.) of nitrogen in pyrolytic graphite. Discussions of the possible interference (i. e., that of boron by the 11B(p, n)11C reaction) will also be given. The nitrogen content of the pyrolytic graphite sample was found to vary markedly according to the starting material and to the preparation conditions.
The Chemistry of Polyazanes. V. The Mechanism of the Oxidation of Benzalphenylhydrazone
Authors: Minato Hiroshi , Tateno Hiroo , Yokokawa Hiroshi
Published: July 2006

Benzalphenylhydrazone was oxidized with amyl nitrite and with sodium hypoiodite, and the products of the oxidation were analyzed. The products identified were dibenzaldiphenyltetrazone, α-benzilosazone and unoxidized benzalphenylhydrazone. The mechanism of the oxidation was discussed.
Organic Sulfur Compounds. XIII. The Reactions of p-Toluenesulfinyl Chloride with Azides
Authors: Kobayashi Michio , Yamamoto Asami
Published: July 2006

Attempts to prepare a sulfinyl azide resulted in the formation of the sulfonyl azide, disulfide, and thiolsulfonate; of these products, the first two were considered to be disproportionation products of the intermediate, sulflnyl azide. The reaction of a sulfinic acid with hydrazoic acid gave a sulfonamide. No rearrangement similar to the Curtius or the Schmidt reaction was observed.
The Ionic Telomerization of Conjugated Diene Compounds. I. The Cationic Telomerization of Butadiene with Its Hydrochlorides at Low Temperatures
Authors: Asahara Teruzo , Kise Hideo
Published: July 2006

The telomerization of butadiene with its hydrochlorides (1-chlorobutene-2 and 3-chloro-butene-1) at low temperatures in the presence of cationic catalysts was investigated. The aim of the present investigation is to’ explore methods to control the molecular weight of the products with various reaction conditions, and to determine the properties and structure of the telomers obtained. The activity of several cationic catalysts at −50–−40°C, and the effects of the conversion and the ratio of chlorobutene to butadiene (RCl/Bu) on the yield and average molecular weights of the telomers were investigated. The products were divided into simple adducts and higher telomers by vacuum distillation. The fraction of the 1 : 1 adduct contained three isomers, one of which was 1-chlorooctadiene-2, 6. The structure and properties of the higher telomers were investigated by the aid of the infrared spectra, the average molecular weight, the iodine value, and elementary analysis. On the basis of the results, the reaction mechanism was discussed.
The Reactions of 1-Chloro-2-oximino-3-butanone
Authors: Masaki Mitsuo , Sugiyama Masatoshi , Tayama Suehiro , Ohta Masaki
Published: July 2006

The reaction of 1-chloro-2-oximino-3-butanone (I) with thiourea at 50–60°C gave S-(2-oximino-3-oxobutyl)thioformamidine hydrochloride (II), which upon being heated in an aqueous solution, then gave 2-amino-4-(1-oximinoethyl)thiazole (III). The treatment of I with amino-acetonitrile gave a mixture of N-(2-oximino-3-oxobutyl)aminoacetonitrile (IV) and N, N-bis(2-oximino-3-oxobutyl)aminoacetonitrile (V), which were confirmed as the corresponding amidoxime and benzoyl or p-nitrobenzoyl derivatives respectively. The reaction of I or 3-chloro-2-oximino-propiophenone with barium thiocyanate gave the corresponding acyclic thiocyanates (VI), while the reaction of anti-bromoacetophenone oxime with barium thiocyanate yielded 2-amino-4-phenylthiazole-3-oxide. That the cyclization reaction between the oximino and the cyano groups of V or VI did not occur seemed to favor the syn-chloromethyl conformation of the oximino group in I, a mechanism for which is hereby proposed.
Studies of the Hydrocracking of Lignin. II. The Components of Lignin Hydrocracking Products
Authors: Oshima Motoyoshi , Kashima Kan , Kubo Teruo , Tabata Haruro , Watanabe Hiroshi
Published: July 2006

The components of the hydrocracking products of alcohol-fermented softwood sulfite waste lignin were identified by rectification, gas chromatography, and IR spectrophotometry. In the acidic fraction (b. p. 170–232°C phenol, o-cresol, 2,6-xylenol, m-cresol, p-cresol, 2-ethylphenol, 2, 4-xylenol, 2, 5-xylenol, 4-ethylphenol, 3-ethylphenol, 3, 5-xylenol, 2-(n-propyl)phenol, 3, 4-xylenol, 4-(n-propyl) phenol and 3-(n-propyl) phenol were identified. In the neutral fraction (b. p. 170–232°C) naphthalene, 2-methylnaphthalene, and tetralin were identified. In the fraction (b. p. 135–170°C) ethylbenzene, m-xylene, p-xylene, o-xylene, and N-propylbenzene were found. In the fraction boiling between 57 and 135°C toluene was identified.
Studies of the Hydrocracking of Lignin. IV. The Evaluation of the Catalysts
Authors: Oshima Motoyoshi , Kashima Kan , Tabata Haruro , Watamabe Hiroshi , Kubo Teruo
Published: July 2006

In order to find a more active catalyst than the standard catalyst (Bull. Chem. Soc. Japan, 39, 2750) (1966)), some seventeen materials were tested in the hydrocracking reaction of lignin. Although no catalyst was found that would alter the economic picture of the process, several interesting pieces of information were obtained. Selenium and zinc iodide gave a very high hydrogen absorption, indicating their activities as the catalyst. The reaction mechanism with these catalysts, seemed, however, very different from that with the standard catalyst. They resulted in high neutral yields and poor phenol yields. Cobalt octacarbonl, cobalt sulfide, ammonium molybdate, Raney iron, iron pentacarbonyl, nickel oxalate, and Ni-S showed fair activities. A closer evaluation of some of the above catalysts revealed that the standard catalyst was, at least at present, the most preferable catalyst.
Fractures in Thin-sectioned Corundum Crystals
Authors: Yamaguchi Goro , Kubo Yasushi , Ogawa Hiroshi
Published: July 2006

The fracture properties of corundum crystals have been examined on various artificial corundums, such as electrically-fused corundum, Verneuil-flame-fused corundum and hydro-thermally-synthetised corundum. The specimens were ground to a tihckness of less than 5/100 mm. The microscope generated in the grinding process were observed by means of a polarizing microscope. The orientation of the c-axis (C) and the crack normal to the section normal (T) was measured using a universal stage. The direction of the crack has a close relation to the crystal orientation of the thin section. Frequent irregular cracks intercrossing one another occur in crystals ground with T∧G angles from 0° to 50°. Cleavage cracks along the {10\={1}1} plane take place prominently in the range of T∧C angles from 50°to 80°. Rare irregular cracks streaming in one direction take place in the range of T∧C angles from 80° to 90°. The heat treatment in air of titania-containing corundum decreases the number of cracks in the crystal. The results have been interpreted on the basis of the cohesion strength theory of M. D. Shappel (Am. Mineralogist, 21, 75 (1936)). In order to explain the limited range of the ocurrence of cleavage cracks, a model has been proposed in which the shearing along the cleavage plane takes place prior to the crack nucleation in the corundum crystal.
Kinetic Studies of Solvolysis. XII. The Question of a Single Mechanism for the “Borderline” SN Reactions—The Solvolysis of Optically Active α-Phenylethyl Chloride in Aqueous Ethanol
Authors: Okamoto Kunio , Uchida Nobuko , Saitô Seiki , Shingu Haruo
Published: July 2006

Competitive solvolysis has been conducted in binary solvents of water and ethanol on optically active α-phenylethyl chloride at 40.0°C. The extents of inversion (α%) for solvolysis products, i. e., α-phenylethyl alcohol and α-phenylethyl ethyl ether, have been calculated from the optical rotations of these products isolated after ten half-lives, and the values of α% have been plotted Vs. the volume percentage of water. In the region of 90% aqueous ethanol, the two α% lines for the alcohol and the ether intersect with each other. This intersection of the two lines conflicts with any single mechanism for the borderline SN reactions, whereas the dual mechanism can explain this phenomenon without any difficulty. In the region of a 100% water-solvent (a typical medium for the SN1 solvolysis), the two lines do not converge to the same α% value. On the basis of these findings, a general mechanism of racemization for the SN1 solvolysis has also been discussed.
The Volatile Constituents of Some Plants of the Compositae Family
Authors: Tsubaki Naoko , Nishimura Kiichi , Hirose Yoshio
Published: July 2006

Full analyses of the essential oils obtained from Yomena (Aster indicus L.), Yomogi (Artemisia princepts Pamp.) and Hog weed (Ambrosia elatior L.) were carried out. Each essential oil was separated by fractional distillation under reduced pressure, and the fractions thus obtained were identified.
The Reactions of cis, trans, trans-1, 5, 9-Cyclododecatriene. IV. Selective Reactions with cis-Addition Reagents
Authors: Ohno Masaji , Okamoto Masaru , Torimitsu Seiichi
Published: July 2006

The addition reactions of cis, trans, trans-1, 5, 9-cyclododecatriene with cis-addition reagents, such as osmium tetroxide, potassium permanganate, diimide, and nitrosyl chloride, have been investigated. It has been shown that the first attack of each reagent preferentially takes place at one of the trans double bonds. The reactions with osmium tetroxide and potassium permanganate at room temperature afforded cis-5, trans-9-cyclododecadiene-trans-1, 2-diol in 89 and 59% yields respectively. The glycol was then further oxidized with osmium tetroxide into cis-y-9-cyclo-dodecene-1, 2, 5, 6-tetrol in a 60% yield. The reduction of the cyclotriene with diimide, generated in situ by the oxidation of hydrazine, afforded cis-cyclododecene in 60—82% yields. The addition of nitrosyl chloride in the presence of hydrochloric acid afforded 2-chlorocyclodode-cadienone oxime in a quantitative yield; this was then reduced into cyclododecanone oxime, obtained in a quantitative yield, by catalytic reduction with palladium-charcoal.
Asymmetric Hydrogenation with Modified Raney Nickel. VI
Authors: Izumi Yoshiharu , Tatsumi Susumu , Imaida Masami , Fukuda Yoshio , Akabori Shiro
Published: July 2006

The asymmetric hydrogenation catalyst has been prepared by the modification of Raney nickel with solutions of (−)-2-methyltartaric acid (A), (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid, and its asymmetric hydrogenation activity has been measured by the hydrogenation of methyl acetoacetate to optically active methyl 3-hydroxybutyrate. The asymmetric activity of the catalyst is much influenced by the pH and the temperature of the modifying solution. Generally, (+)-2-methyltartaric acid (B) and (+)-2,3-dimethyltartaric acid have a high asymmetric activity in reaction to Raney nickel. The highest asymmetric activity has been obtained by modification with (+)-2-methyltartaric acid (B) and with it the specific rotation of the hydrogenation product has been found to be [α]D20 +11.72° (without a solvent) under the optimum conditions. This value means that the product is 78% composed of the dextro- and 22% of the levorotatory form. On the other hand, the asymmetric activity of the catalyst modified with (−)-2-methyltartaric acid (A) is very low and quite different from that of the catalyst modified with (+)-2-methyltartaric acid (B). It has been supposed that this difference depends on the stereoisomerism of the threo-erythro form of the 2-methyltartaric acid molecule.
The Transfer of the Oxygen Atom of Water in an Aqueous Solution of Iron and Copper Sulfates
Authors: Suzuki Nobutake , Hotta Hiroshi , Hashimoto Hitoshi
Published: July 2006

When an oxygen-18 enriched aqueous solution of ferrous, ferric and cupric sulfates was heated between 130 and 200°C, the oxygen-18 content decreased in the order of FeII>FeIII>CuII in water; and it increased in the sulfate group and in the molecular oxygen of the gaseous phase. A transfer of oxygen from water to the sulfate group was also observed, even in a nitrogen atmosphere. The oxygen transfer was promoted in all the cases in the presence of molecular oxygen, and it increased further in the presence of benzene. Since the exchange reaction of oxygen does not occur between water and sulfate ions, the above facts may be attributed to the reactions between water and the thermal decomposition products of the sulfate group, and between water and the hydrogen peroxide produced. The peroxy species, produced by the oxidation of the decomposition products, are more reactive in such a transfer of oxygen, since the reaction is promoted in the presence of oxygen. The peroxides in the autoxidation of benzene seem also to be reactive in it.
Silent Discharge Reactions in Aqueous Solutions. I. An Acidic Aqueous Solution of Ferrous Sulfate in Atmospheres of Helium and Argon
Authors: Yokohata Akira , Tsuda Satoru
Published: July 2006

In an atmosphere of helium or argon, the silent discharge reactions of aqueous solutions have been investigated from the point of view of radiation chemistry. A discharge tube with two coaxial glass tubes was used. In a dilute oxygen-free aqueous solution of sulfuric acid, hydrogen peroxide appeared as a result of discharge. Also, the oxidation of ferrous ions to ferric ions has been found. It has been confirmed, first, that neither the effect of metastable excited states of helium and argon nor that of luminescence is serious, and, second, that the reaction may well be interpreted by taking into consideration the actions of slow electrons generated in the gas phase on the liquid water. The yield of hydrogen atoms plus hydroxyl radicals has been estimated from the yields of hydrogen peroxide and ferric ions. The ratios of the yield of hydrogen peroxide to that of radicals show that the silent discharge reaction corresponds to the reaction by ionizing radiation of high LET, the value of which apparently equals 3eV./Å in helium and 8 eV./Å in argon. The G(Fe3+) value and the absorbed dose (E) estimated were, respectively, as follows: In helium: G(Fe3+)=4.6, E=3.8×106 r./hr.; in argon: G(Fe3+)=4.3, E=7.2×106 r./hr.
The Absorption Spectra of Dyes. X. Note on the Configuration of the Component Molecules in the Complex State
Authors: Hoshi Toshihiko , Tanizaki Yoshié
Published: July 2006

The configuration of the component molecules in the complex formed between Chryophenine G (G) and the direct dyes (P),such as Chlorazol Sky Blue FF, has been discussed qualitatively with respect to the relation between the steric structure of the individual P molecules and the enthalpy or the entropy changes in the complex formations. the electrons to be transferred from the partner (P) to the G molecule are the π electrons of the functional (hydroxy) groups and are those of the inner-side groups when the respective coupling components of the dye have more than one functional group. The large the charge density of such an effective functional group becomes, the more the enthalpy change (−ΔH) is increased. It may be said with certainty that there must exist a certain configuration of the component molecules peculiar to the complex formation. Such a configuration may be seen for the configuration of G and ND (NW-acid←dianisidine→NW-acid). For other combinations of which the partner of G is more deformed in free than ND state, the shifts of equilibrium to the configuration for the complex state are almost due to an entropy change (−ΔS) which increases in proportion to the magnitude of the deformation.