bluuebunny/crossref_metadata_2025 huggingface dataset:
Phase Transitions in Crystalline Divalent Metal Dicalcium Propionates. I. Calorimetric and Dielectric Investigations of Strontium- and Lead Dicalcium Propionates
Authors: Nakamura Nobuo , Suga Hiroshi , Chihara Hideaki , Seki Syûzô
Published: July 2006

Heat capacities have been measured for strontium and lead dicalcium propionates from 15 to 300°K with an adiabatic-type calorimeter in connection with the ferroelectric phase transition of strontium salt. The heat capacities, enthalpies, entropies and Gibbs energy functions in the standard state have been determined. For the strontium salt, the transition temperature, the heat of transition, and the entropy of transition for the ferroelectric phase transition are 282.6°K, 159.6 cal.mol−1, and 0.6 e.u. respectively. Another phase transition was discovered at 104°K; the heat and entropy of this transition amount to 255 cal.mol−1 and 3.2e.u. respectively.

For the lead salt, a phase transition was found at 191.5°K, and the heat and the entropy of the transition are 1160.0 cal. mol−1 and 5.8 e.u. respectively. Low frequency dielectric constants have been measured for the lead salt from the liquid nitrogen temperature to 90°C. A discontinuous change in the dielectric constants at 183°K and another dielectric anomaly at 60°C have been observed. The absence of evidence of ferroelectricity above room temperature has also been confirmed.

The ferroelectric phase transition of the strontium salt has been treated by the Bragg-Williams theory. The temperature dependence of the spontaneous polarization has tentatively been interpreted with torsional oscillations of the methyl groups of the propionate anions.
The Copolymerization of the Vinyl Monomer with a Cyclic Compound. II. The Cationic Copolymerization of Some Vinyl Monomers with β-Propiolactone
Authors: Aoki Shuzo , Harita Yoshiyuki , Otsu Takayuki , Imoto Minoru
Published: July 2006

The copolymerization of several vinyl monomers, such as styrene (St), α-methylstyrene and isobutyl vinyl ether, with β-propiolactone (β-PL) as catalyzed by Lewis acids has been investigated in methylene chloride at 0°C. In the copolymerization of β-PL and St using boron trifluoride-diethyl etherate or stannic chloride as a catalyst, the copolymer was obtained. The apparent monomer reactivity ratios were estimated to be as follows:

r (β−PL)=0.2; r(St)=20

In the other copolymerization systems, the copolymer was not obtained. The mechanism of these copolymerizations has been discussed.
The Catalytic Hydrogenation of Aniline
Authors: Hagihara Hiroshi , Echigoya Etsuro
Published: July 2006

1) The order of the activity of a metal catalyst for the hydrogenation of aniline is Co>Ni>Fe, Cu. The order of their selectivity is Co>Ni.

2) The activity of the mixed metals (Co-Ni, Co-Fe) is lower than that of a cobalt single catalyst.

3) The rate of hydrogenation increases with the temperature up to 180–200°C, and then decreases at higher temperatures. This phenomenon may be explained in terms of the kinetics of the reaction.

4) The catalyst which consists of a complex between the metal and its carrier-oxide is less active than the free metal catalyst for the hydrogenation reaction, and it almost completely loses its activity for the hydrogenolysis reaction.

5) The production of cyclohexylamine is affected by the property of the carrier oxide.

6) The main course of the production of dicyclohexylamine is considered to proceed through the condensation of two cyclohexylamine molecules and through N-cyclohexylidene-cyclohexylamine.

Notation:r. p. c.=relative partial charge on the oxygen of oxide (reported by R. T. Sanderson)

−ΔH0°=standard heat of formation of the higest oxide per metal g.-atm.
Surface Chemistry of the Polyamide Series. I. Effect of Hydrogen Bonding on the Nature of Poly-α-amino Acid Monolayers
Authors: Yamashita Takuya , Isemura Toshizo
Published: July 2006

The effect of hydrogen bonding on the nature of poly-α-amino acid monolayers has been studied at the air/water and oil/water interfaces with poly-l-alanine, poly-Dl-alanine, polysarcosine, copoly-1 : 1-(glycine, sarcosine), copoly-1 : 1-(Dl-alanine, sarcosine) and poly-α-aminoisobutyric acid.

Poly-l-alanine and poly-Dl-alanine gave monolayers of the condensed type on distilled water, and the surface viscosity of poly-Dl-alanine was first detected at a much larger area than its close-packed area where the surface pressure was sufficiently low. This fact suggests that there exists a strong interaction between peptide bonds of polyalanine. Both polymers would assume a β-configration. On the concentrated sulfuric acid subsolutions, the film of poly-Dl-alanine was expanded and an increase in surface moment was observed because of the breaking of hydrogen bonds between peptide linkages.

A steric hindrance to the hydrogen bond formation was observed with the film of poly-α-amino isobutyric acid. This polypeptide gave an expanded monolayer on distilled water, and its surface viscosity could be first detected at a very small area where the surface pressure was remarkably high.

The film of copoly-1 : 1-(Dl-alanine, sarcosine) was of the expanded type on the 3 m potassium chloride subsolution because of the decrease in the number of hydrogen bonds and that in the double-bond nature of the main chain.

At the oil/distilled water interface, a marked difference was found between the monolayers of poly-Dl-alanine and polysarcosine, although these polymers have the same side chains. Poly-Dl-alanine gave a considerably condensed monolayer, even at the oil/water interface. On the other hand, the film of polysarcosine was of the expanded type. The difference between the films of these polymers is mainly to be ascribed to the presence or the absence of hydrogen bonds. The 1 : 1-copolymer of sarcosine with glycine or Dl-alanine also gave an expanded monolayer.
Photoelectric Emission and Electrical Conductivity of the Cesium Complex with Pyrene Derivatives
Authors: Ogino Kyohei , Iwashima Satoshi , Inokuchi Hiroo , Harada Yoshiya
Published: July 2006

On the basis o the charge transfer process of the complexes, the photoemission and the electronic conduction of the complexes between cesium and pyrene derivatives, tetranitropyrene (TNO2P), tetrachloropyrene (TClP), tetrabromopyrene (TBrP) and tetracyanopyrene (TCNP) have been measured. A strong increase in the quantum yield of photoemission, from 10−3–10−4 to 10−1–102, resulting from the formation of the complexes, has been found. The promotion may take place by means of an electron transfer from cesium metal to a partner molecule; [Cs+] [Aromatics−]. The assumption is supported by the findings concerning electron spin resonance absorption and charge-transfer spectra.

The electrical resistivity of the complexes, ρ at 15°C of pyrene-Cs=2.1×104 Ωcm., (TClP)-Cs=8Ωcm., (TBrP)-Cs=1.6×101 Ωcm., (TNO2P)-Cs=2×106 Ωcm. and (TCNP)-Cs=6×105 Ωcm., is strongly affected by the contribution of the, dative-bond character of the complexes.
Studies of Mixed Cyano Cobalt(III) Complexes. I. The Cyano-Diamine Series
Authors: Ohkawa Kuwako , Fujita Junnosuke , Shimura Yoichi
Published: July 2006

Several new mixed cyano-diamine complexes, M[Co(CN)4en]·xH2O (M=K, x=1; M=Na, x=3.5), Ba[Co(CN)4tn]2·4H2O, [Co(CN)2pn2]2S2O3·H2O and [Co(CN)2tn2]2S2O3, have been prepared, and their infrared, visible and ultraviolet absorption spectra have been determined. From these spectral results, it has been concluded that the two dicyano complexes are cis isomers.

No remarkable Cotton effect has been observed in the region of the spin-forbidden band of the cis-[Co(CN)2en2]+.
The Hydroesterification of Propylene with Carbon Monoxide and Methanol in the Presence of Dicobalt Octacarbonyl
Authors: Matsuda Akio , Uchida Hiroshi
Published: July 2006

Propylene can be hydroesterified to methyl butyrate in a good yield and with an initial rate as high as the initial rate of the hydroformylation of propylene, provided a small amount of hydrogen and excess pyridine are present. Detailed data on the initial rates at the zero-conversion of propylene for both the hydroesterification and hydroformylation and the ratio between the two initial rates have been presented as a function of the amount of pyridine and hydrogen, together with data on the products obtained from the respective reactions.

The initial rate of hydroesterification in this study has proved to be first-order with respect to the propylene concentration. This result is different from that of Ercoli et al., who carried out hydroesterification runs of olefins with pure carbon monoxide.
The Chemiluminescence, Fluorescence and Absorption Spectra of 2,4,5-Triphenylimidazole
Authors: Maeda Koko , Ojima Heijiro , Hayashi Taro
Published: July 2006

The chemiluminescence spectra of 2,4,5-triphenylimidazole (lophine) in 1n ethanolic potassium hydroxide exhibited with oxygen and with hydrogen peroxide at 70°C have been measured. Both spectra spread, over about 470–660 mμ; the maximum wavelengths are 545 mμ and 555 mμ respectively.

The fluorescence spectra of solutions of lophine have been measured at 70°C. The maximum wavelengths are as follows: 371 mμ, 388 mμ (ethanol), 441 mμ (1n KOH–C2H5OH) and 391 mμ (1 n CH3COOH–C2H5OH).

The absorption spectra of lophine have also been measured: λmax 303 mμ (ε= 2.56× 1O4) in ethanol: λmax 326 mμ (ε=3.33×104) 1n ethanol potassium hydroxide, and λmax 295 mμ (ε=2.03×104) in a 1n solution of acetic acid in ethanol.
Acid and Basic Hydrolyses of p-Nitrophenyl Benzenesulfonate
Authors: Oae Shigeru , Kiritani Reiko
Published: July 2006

The mechanisms of both the acid- and the alkaline-catalyzed hydrolyses of p-nitrophenyl benzenesulfonate have been investigated by means of the 18O-tracer technique. The acid-catalyzed hydrolysis apparently proceeds via a SN2-type process involving the nucleophilic attack of water on the sulfur atom, with a S–O bond cleavage. Much as with the earlier findings concerning other nucleophiles, the major portion of the alkaline hydrolysis was also found to proceed through a SN2 process which involves the nucleophilic attack of the hydroxide ion on the sulfur atom, with a S–O bond fission; only a small portion of the reaction appeared to proceed via an aromatic SN2-type process.
Studies of the Organic Reactions of Metal Carbonyls. VI. The Isomerization of Acylcobalt Carbonyls—The Effects of Solvents and of the Structure of the Acyl Group
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa , Masada Hiromitsu , Okuda Yasukazu
Published: July 2006

The reactions of n-butyryl chloride, isobutyryl bromide, α-ethylbutyryl chloride and n-caproyl chloride with potassium cobalt carbonylate have been studied. The results of this investigation are as follows.

(1) It has been observed that solvents have great effects on the isomerization of butyrylcobalt carbonyls, as do the reaction temperature and the atmosphere. The rate and the equilibrium of this isomerization are remarkably affected by the solvents; in polar solvents, the equilibrium proportion of products (iso/normal) is almost zero in dioxane, 1/3 in ethyl acetate, and 1 in diethyl ether. This isomerization proceeds more rapidly under nitrogen atmosphere than under carbon monoxide. On the other hand, in nonpolar solvents such as benzene this isomerization apparently does not occur.

(2) α-Ethylbutyrylcobalt carbonyl relatively readily isomerizes to n-caproylcobalt carbonyl. This isomerization is also accelerated under nitrogen atmosphere.
Direct Preparation of Partially Fluorinated Methane
Authors: Nagase Shunji , Tanaka Kiyoshi , Baba Hajime
Published: July 2006

Partially fluorinated methanes were obtained directly from methane in a reasonable conversion and current efficiency by electrochemical fluorination, using a cell equipped with a bubbling arrangement. This fluorination unit worked satisfactorily for controlling the fluorination reaction of gases slightly soluble in hydrogen fluoride.

Performance and effect of the bubbler, and the effect of sample feed rate, electrolysis temperature, dilution of the sample with helium, the amount of sodium fluoride, and the anodic current density, on the fluorination reaction are described and discussed in detail.
The Preparation of Heavy Metal Hydride and Its Catalytic Activity. VIII Information on the Mechanism of Iron Hydride Formation
Authors: Takegami Yoshinobu , Ueno Toru , Kawajiri Kiyoshi
Published: July 2006

Some information on the mechanism of iron hydride formation in the reaction of iron (III) chloride with phenylmagnesium bromide under a hydrogen atmosphere has been presented. When the molar ratio (C6H5MgBr/FeCl3) is larger than 5, 3–4 (mol./mol. FeCl3) of hydrogen is absorbed during the synthesis of hydrides. The amounts of benzene, one of the by-products formed in the synthesis, have also been determined. The treatment of these hydrides with styrene under a nitrogen atmosphere has given ethylbenzene in amounts which correlate well with the amounts of hydrogen absorbed during the hydride synthesis. These observations can be taken as support for the formation of iron hydride. On the other hand, a mixture prepared by the reaction of iron(III) chloride with phenylmagnesium bromide under a nitrogen atmosphere evolved about 0.5 (mol./mol.FeCl3) of hydrogen on hydrolysis. When the hydride prepared under a hydrogen atmosphere was hydrolyzed with dideuterosulfuric acid, D2 as well as HD was evolved. These results seem to indicate that not only hydride sites but also metallic sites were formed during the iron hydride synthesis. On the basis of these observations, a possible mechanism for the formation of complex hydride containing iron and magnesium has been presented.
The Conversion of Cellulose into Soluble Glucose Polymers in a Sulfur Dioxide Solution of Sulfur Trioxide
Authors: Sakai Yoshio
Published: July 2006

The conversion of cellulose into soluble glucose polymers was shown to be composed of a set of irreversible reactions in series: A\xrightarrowk1B\xrightarrowk2C, where A is cellulose; B, a soluble glucose polymer, and C, the decomposition product, which does not give reducing sugar under further hydrolysis by dilute acid. The first-order rate constants, k1 (hr−1) and k2 (hr−1), were given in 0.32 to 3.3% sulfur dioxide solutions of sulfur trioxide:

k 1=2.64×1011C1.63exp[−16700⁄(RT)] (for 0–50°C),

and k2=8.99×1015C1.63exp[−24500⁄(RT)] (for 25–50°C),

From k1 and k2, the sulfur trioxide concentration, C, and temperature, T, the maximum yields of the soluble glucose polymer and the time required to attain a maximum yield were obtained. It was shown that the application of the technique to wood saccharification is possible.
The Polarographic Investigation on the Reaction between Chromium(II)-ethylenediaminetetraacetate and Nitrate Ions
Authors: Tanaka Nobuyuki , Ito Tasuku
Published: July 2006

The effect of nitrate ions on the polarographic waves of ethylenediaminetetraacetatoaquochromate(III) ions has been studied in acetate buffer solutions and acid potassium chloride solutions. Nitrate ions are chemically reduced in the vicinity of the mercury drop of the electrode by chromium(II)-EDTA complexes which are formed by the electroreduction of chromium (III)-EDTA complexes. The chromium (III)-EDTA complexes thus formed are reduced again at the DME and the intermediate products of nitrate ions are reduced further chemically with chromium (II)-EDTA complexes or electrochemically, resulting in the enhancement of the current. The nature of the limiting current is investigated and compared with that predicted from the theoretical treatment. The reaction between chromium(II)-EDTA and nitrate ions has also been investigated in acetate buffer solutions and its rate constant, 35 1. mol−1 sec−1 at nearly 0°C, μ=0.1, has been compared with 30 l. mol−1 sec−1, the value obtained from the polarographic catalytic current under almost the same condition.
The Autoxidation of α-Methylstyrene in the Presence of Metal Salt
Authors: Niki Etsuo , Kamiya Yoshio
Published: July 2006

The azobisisobutyronitrile-initiated autoxidation of α-methylstyrene in the presence of metal salt was studied from the viewpoints of rate and products. The over-all activation energy was found to be 19.7 kcal./mol. In most cases, metal salts had a retarding effect on the rate of oxidation. With manganese and copper salts, an increase in the concentration of the metal decreased the rate of oxidation monotonously. However, cobalt naphthenate had an accelerating effect within a limited range of concentration, although it also had an inhibiting effect at higher concentrations. The products were acetophenone, formaldehyde, α-methylstyrene oxide and α-methylstyrene polyperoxide. Metal salt had little effect on the products of oxidation, with the exception of cobalt salt, which gave α-methylstyrene oxide in considerable yield even at 760 mmHg of oxygen pressure, where little α-methylstyrene oxide was formed in the presence of other metal salts or in the absence of catalysts.
Reactions of 2-Chlorocycloalkanone Oximes. II. Syntheses of 3-Aminocycloalka[C]isoxazoles
Authors: Ohno Masaji , Naruse Norio
Published: July 2006

The displacement reactions of α-chlorocycloalkanone oximes with sodium cyanide in dimethyl sulfoxide or ethanol have been studied. It has been shown that 3-aminocycloalka[C]-isoxazoles can be obtained in excellent yields. α-Chlorooximes of cyclohexanone, cyclooctanone, cycloocten-5-one, cyclododecanone, and cyclododecadien-5, 9-one have been subjected to the reaction, affording the corresponding isoxazole derivatives in 48, 96, 89, 95, and 90% yields respectively. The application of the method to 3-chloronorcamphor oxime and α-chlorooximes from acyclic olefins afforded cyanooximes; it failed to give isoxazole derivatives. The hydrogenation of 3-aminocycloocta[C] isoxazole gave 2-amino-1-cyclooctanecarbonamide by the hydrogenolysis of the nitrogen-oxygen bond of the isoxazole ring system. The amino-carbonamide was treated with either the base or acid to give 2-oxycyclooctanecarboxylic acid.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. VI. The Synthesis of Ser1- and Gly1-Decapeptides Corresponding to the First Ten-amino-acid Sequence of Corticotropin
Authors: Otsuka Hideo , Inouye Ken , Shinozaki Fusako , Kanayama Makoto
Published: July 2006

t-Butyloxycarbonyl-seryl-(and-glycyl-)tyrosyl-seryl-methionyl-glutamyl-histidyl-phenylalanyl-arginyl-tryptophyl-glycine have been synthesized as the first step of the synthesis of adrenocortico-tropically active peptides. The trifluoroacetic acid treatment of these two compounds afforded the free decapeptides, seryl-tyrosyl-seryl-methionyl-glutamyl-histidyl-phenylalanyl-arginyl-tryptophyl-glycine, which corresponded to the amino-acid sequence of positions 1 to 10 in the corticotropin molecule, and its glycine1-analog. Concerning the synthesis of serine peptides, a tetrapeptide derivative, corresponding to the first four amino acid residues of corticotropin, was obtained by using O-benzyl-serine.
Amino Acid-Carbohydrate Coordinated Compounds. II. The Synthesis and the Stability of 3-O-Aminoacyl-d-glucoses
Authors: Muramatsu Nobutoshi
Published: July 2006

3-O-Aminoacyl-d-glucoses (amino acids; Gly, l-Ala, l-Lys, l-Asp (α and β) and l-Glu (α and γ)) have been prepared by the condensation of 1,2; 5,6-di-O-isopropylidene-d-glucose with suitably protected amino acid derivatives in the presence of N,N′-dicyclohexylcarbodiimide, followed by the removal of the protected groups. The effect of free amino and carboxyl groups on the stability of these compounds has been clarified.
Organic Sulfur Compounds. VIII. The Formation of Sulfinate Esters by the Alkylation of Sulfinic Acid Salts
Authors: Kobayashi Michio
Published: July 2006

The alkylation of the sulfinic acid salts with triethyloxonium fluoroborate results in the formation of the ethyl sulfinates, not in the usual sulfone formation.
The Sensitive Gas Chromatography of Para-, Orthohydrogen, Hydrogen Deuteride and Deuterium
Authors: Yasumori Iwao , Ohno Seigo
Published: July 2006

A sensitive gas chromatograph of the reduced-pressure type was devised to analyze hydrogen nuclear spin isomers and isotopes, and its characteristics were studied in order to obtain the optimum conditions for analysis. It was shown that the para and ortho composition of 0.01 ml. S. T. P. of normal hydrogen could be determined within an accuracy of 1% by employing an alumina column cooled at −196°C, while the composition of 0.02 ml. S. T. P. of the equilibrated mixture of hydrogen, hydrogen deuteride and deuterium at 25°C could be determined within the same accuracy by employing an alumina column coated with manganese chloride. The alumina column was no longer capable of separating the spin isomers when it was treated above 350°C. Kinetic studies of the hydrogen-deuterium equilibration (21°C) and of the orthohydrogen conversion (−196°C), using the alumina as a catalyst, revealed that this strong activation creates active sites for the equilibration and the magnetic conversion which makes the peak separation obscure. The nature of these active centers was briefly discussed.
The Crystal and Molecular Structure of the Dehydrated Tetramer of 1,2-Dimethyldisilanetetraol, (CH3)8Si8O8
Authors: Higuchi Taiichi , Shimada Akira
Published: July 2006

The crystal and molecular structure of (CH3)8Si8O8 has been determined by means of the Patterson projections and refined by the two-dimensional Fourier technique and the least-squares method. The space group is P4/nnc, with four molecules per unit cell. The unit cell constants are a=11.73±0.02 Å, and c=17.17±0.02 Å. The skeleton of a molecule consists of two “crown-shaped” (–Si–O–)4 rings which are crystallographically independent of each other and are connected by four Si–Si bonds along the c axis. The four six-membered (–Si–Si–O–)2 rings thus formed have boat forms. Hence, a molecule forms a cage-like conformation with an approximate symmetry of 4/mmm. Each molecule in the unit cell is surrounded by four adjacent molecules related with centers of symmetry; these molecules form, in a sense, a layer perpendicular to the c axis.
The Adsorption Equilibria of Dl-Mandelic Acid on Starch in an Aqueous Phase
Authors: Ohara Masaaki , Chen Chau-Yang , Kwan Takao
Published: July 2006

The selective adsorption of d- or l-mandelic acid on starch from an aqueous solution of racemate has been quantitatively investigated. l-Mandelic acid has been judged from the distinct negative value of the optical rotation in the solution to be adsorbed preferentially over the d-isomer. The separation factor for the adsorption of the two enantiomers was 1.06±0.02 at 0°C. From the saturation value estimated by the Langmuir equation for adsorption, the ratio of the glucose residue to the Dl-mandelic acid adsorbed has been calculated as 5, indicating that not all the glucose residues in the starch constitute adsorption sites for mandelic acid.
The Basicities of Tropone and Tropolone
Authors: Hosoya Haruo , Nagakura Saburo
Published: July 2006

The ultraviolet absorption spectra of tropone (I) and tropolone (II) were measured with sulfuric acid solutions of various acidities. The accurate pKa values, as determined by the proposed method, were −1.02 and −0.86 for I and II respectively. The Raman spectra of II were measured with sulfuric acid solutions of various acid concentrations. The bands in the 6 and 15 μ regions change sharply when the solvent acidity changes from 5 to 25%, corresponding well to the ultraviolet absorption change. The infrared absorption spectra of II were measured with the concentrated deuterosulfuric acid solution in the 6 μ region. The vibrationals mode of the protonated tropolone were discussed.
Nuclear Magnetic Resonance Spectra of Polyethylene
Authors: Kato Yoshinori , Nishioka Atsuo
Published: July 2006

A quantitative study of some structural irregularities of polyethylenes by an improved proton magnetic resonance method is reported. The background noise of a nuclear magnetic resonance spectrometer can be remarkably eliminated with the aid of the Mnemotron Computer of Average Transients. The total numbers of methyl groups in polyethylenes were estimated by this method using 5% solutions of the polymer in tetrachloroethylene. Spectra were obtained at about 110°C in order to suppress the thermal degradation of the polymer. The results agree well with those estimated by an infrared compensating method. Information about the species of branches and, in some cases, the number-average molecular weight of the polymer can be obtained by examining the resonance shape of methyl groups. The chemical shift difference between the triplet due to ethyl branches and that due to the other longer branches was found to be less than 0.05 p.p.m. This method can also be applied to the detection of unsaturations in polyethylene. In this case, however, the signal-to-noise ratio has to be increased to a factor of at least 20. Thus, the purification of the solvent is very important in the experiment.
Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of Some Carboxylic Esters
Authors: Yoshikawa Sadao , Kim Oh-Kil
Published: July 2006

The catalytic effects of polymeric sulfonic acids in ester hydrolysis in aqueous acetone were inferior to that of hydrochloric acid. However, the hydrolysis rate was accelerated by increasing the water content of acetone-water mixtures, and, in a water solution, polymeric sulfonic acids were much more effective catalysts. Furthermore, the catalytic efficiency of polymeric sulfonic acid in ester hydrolysis in water increased with the length of the ester molecule. The polymeric sulfonic acid with a strong hydrophobic character was more effective; 69% sulfonated polystyrene-sulfonic acid, for example, hydrolyzed methyl hydrogen azelate in water over five times more rapidly than hydrochloric acid. The specificity thus obtained suggests that, in the hydrolysis of electrically-neutral esters in water, ester molecules are concentrated in the neighborhood of the polymer by the hydrophobic interaction between catalyst and substrate. Besides, in the hydrolysis of aliphatic esters catalyzed by polyvinylsulfonic acid in 50% aqueous acetone, there was a linear relationship between the reciprocal of the rate constant and the intrinsic viscosity of the polymer, while in the case of polystyrenesulfonic acid hardly such any relationship was found. These remarkably different behaviors of the two kinds of polymer catalysts should be attributed to the difference in the expansion of the polymer chain in solutions.
Organoboron Compounds. X. On the Reaction of o-Hydroxybenzeneboronic Acid Anhydride with Some Sulfonamides
Authors: Kato Seiji , Kimura Keiko , Nagata Katsuhisa , Tsuzuki Yojiro
Published: July 2006

Several new azo compounds containing boron atoms have been synthesized by the use of sulfonamides; these compounds have an excellent effect on bacilli. It was expected that the antibiotic effect would be very remarkable, since it had been reported that boron-containing azo dyes are useful for therapy on brain tumors. A mixed solvent of ethanol-water (1:1) and acetone was found useful for recrystallizing this class of compounds. The infrared spectra of these compounds show absorption bands at the 1090—1100cm−1, 1375—1380 cm−1 and 1600—1610 cm−1 regions these bands may be assigned to the carbon-boron, boron-oxygen and nitrogen-nitrogen bonds respectively.
Perchloro-(dimethylene-1,2-cyclobutanedione) and Its Solvolytic Degradation
Authors: Fujino Akira , Kusuda Kousuke , Sakan Takeo
Published: July 2006

Perchloro-(3,4-dimethylenecyclobutene) has been converted to 1, 3′, 3′, 4′, 4′-pentachloro-2-methoxy-3,4-dimethylenecyclobutene; in some solutions exposed to the air, this then gradually decomposed to perchloro-(dimethylene-1, 2-cyclobutanedione). The further spontaneous degradation of the last compound in an aqueous ethanol solution has also been investigated in order to elucidate the structures of an unstable intermediate (an adduct of ethanol to the carbonyl) and the end product (the hemi-ketal lactone ester). The physical and chemical properties of these compounds have been given and discussed. A possible bicyclic intermediate caused by the interaction between the hydroxyl group and the diagonally-positioned dichloromethylene group in above unstable ethanol adduct has been suggested in the process from the latter compound to the end product.
The Chemistry of Protactinium. II. The Behavior of Pentavalent Protactinium in a Perchloric Acid Solution
Authors: Suzuki Shin , Inoue Yasushi
Published: July 2006

Studies of the chemical behavior of protactinium(V) were carried out with the TTA-benzene extraction method, the ion exchange method and the filtration method. When the protactinium concentration is less than 10−6  m and the perchloric acid concentration is 0.3—2.0 n, the reaction of TTA extraction may proceed as:

PaOm(OH)n5−2m−n+4HT\ightleftarrowsPa(OH)T4+(m+n−1)H2O+(5−2m−n)H+

where 2m+n is 3 and 4, or as:

PaOm(OH)nT4−2m−n+4HT\ightleftarrowsPaT5+(m+n)H2O+(4−2m−n)H+

where 2m+n is 2 and 3.

The cation exchange experiment gives results consistent with this conclusion. On the other hand, when the concentration of protactinium is higher than 10−6  m, the above relation does not hold, even in the 5 n perchloric acid solution, because protactinium forms the aggregates to a great extent. This has been confirmed by the filtration experiment.
Compounds Related to Imido-Substituted Ethylenes. I. The Preparation of Diimido-Substituted Ethylenes
Authors: Tsuge Otohiko , Yanagi Kiyoshi , Fukuhara Sh\={o}ji
Published: July 2006

Methods for the preparation of cis-, trans-1, 2-diphthalimidoethylene, its nitro derivative, 1,1-diphthalimido- and 1, 2-bis(o-sulfobenzimido)ethylene are described. In this connection, the thermal, irradiated and iodine-catalyzed isomerization of cis- and trans-1, 2-diphthalimidoethylene have also been studied in detail.
Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of the Amino Ester and Related Compounds
Authors: Yoshikawa Sadao , Kim Oh-Kil
Published: July 2006

The amino ester hydrolysis by polymeric sulfonic acids increased as the concentration ratio, Cester/Cacid, was lowered, and a maximum in the plot of the rate constant, k, against the Cester/Cacid ratio was attained near the ratio=0.4 in the case of the β-alanine methyl ester as well as in the case of γ-methyl l-glutamate. At this optimum concentration, the catalytic effect of polyvinylsulfonic acid (A), for example, in the hydrolysis of the β-alanine methyl ester was 16 times greater than that of hydrochloric acid, while the effect of polystyrenesulfonic acid was about 7 times greater. The catalytic effects of hydrochloric acid and ethanesulfonic acid were the same in all cases, and there was no such specific behavior as in the former. Furthermore, the catalytic efficiency of polyvinylsulfonic acid in amino ester hydrolysis increased with an increase in the polymer molecular weight, in contrast with the case of the carboxylic ester, while no such correlation was found in the polystyrenesulfonic acid. Besides, the catalytic effect of partially-neutralized polymeric sulfonic acid, polyvinylsulfonic acid especially, decreased remarkably with the degree of neutralization. These different kinds of behavior can be interpreted as being due to the difference in the expansion in solutions and in the geometrical distances between nearest-neighboring sulfonic acid groups on the polymer chain.
Multiple Charge-transfer Bands of the Pyrene-Tetracyanoethylene Complex
Authors: Kuroda Haruo , Ikemoto Isao , Akamatu Hideo
Published: July 2006

The polarized absorption spectra of the single crystal of the pyrene-tetracyanoethylene complex have been observed by means of a microspectrophotometer. It is shown that two absorption bands, at 12700 cm−1 and 20000 cm−1 respectively, are polarized along the c-axis, the direction connecting the molecular center of the donor and that of the acceptor; hence, both have been assigned to the charge-transfer bands. The interactions of 32 possible charge-transfer states with the no-bond state are discussed in terms of the simple molecular orbital theory, and their contributions to the energy of the complex formation are compared with each other. It is revealed that the interactions of higher charge-transfer states are relatively important and can not be neglected compared with that of the lowest charge-transfer state, and that the appearance of the multiple charge-transfer bands is a natural consequence of such a configurational interaction. It is also suggested that the ratio of the intensities of the first and the second charge-transfer bands may be a parameter that offers information on the orientation of the donor molecule to the acceptor molecule. A probable model is proposed for the structure of the pyrene-tetracyanoethylene complex formed in the solution.
Aminocyclitols. X. A Synthesis of Deoxyinosamine and Deoxyinosadiamine and Their Nuclear Magnetic Resonance Spectra
Authors: Suami Tetsuo , Yabe Kenji
Published: July 2006

(±)-1-Deoxy-muco-inosamine-4, (±)-1-scyllo-inosamine-2 and (±)-2-deoxy-allo-inosadiamine-3, 5 pentaacetates have been synthesized from 1-deoxy-myo-inositol (I). The hydroxyl groups of I are mesylated, and the mesyloxy groups are replaced by azido groups. The reduction of the azido compounds, followed by acetylation, gives the pentaacetyl-deoxyinosamines and deoxyinosadiamine. Their structures have been established by means of a study of the proton magnetic resonance spectra.
The Anionoid Substitution Reaction of Diethyl 2-Acetamido-6-bromoazulene-1, 3-dicarboxylate
Authors: Tada Masao
Published: July 2006

The bromine atom in diethyl 2-acetamido-6-bromoazulene-1, 3-dicarboxylate (I) is as reactive toward the anionoid reagents as in diethyl 6-bromoazulene-1, 3-dicarboxylate. Twentyseven 6-substituted azulene derivatives have been synthesized from I by the nucleophilic substitution reaction. On one of them, diethyl 2-acetamido-6-diethylaminoazulene-1, 3-dicarboxylate, the removal of the 2-acetamido group has been carried out, giving diethyl 6-diethylaminoazulene-1, 3-dicarboxylate.
Benzo-1, 4-thiazino[3,2-b]tropone 5-Oxides and 5, 5-Dioxides
Authors: Nozoe Tetsuo , Asao Toyonobu , Takahashi Kazuko
Published: July 2006

The oxidation of benzo-1, 4-thiazino[3,2-b]tropone and its 8-isopropyl derivative with hydrogen peroxide afforded the corresponding 5-oxides or 5, 5-dioxides. The stability of these oxides to heating, acid and alkali was examined. The bromination or nitration of these oxides gave mainly 9-bromo or 9-nitro derivatives. 7- or 9-Aminobenzo-1, 4-thiazino[3,2-b]tropones were obtained by the reduction of the corresponding nitro compounds.
Studies of Aminosugars. XIII. The Synthesis of Paromamine
Authors: Umezawa Sumio , Koto Shinkiti
Published: July 2006

Paromamine has been synthesized by condensing the N,N′-dinitrophenyl derivative of deoxystreptamine with the N-dinitrophenyl derivative of acetobromoglucosamine in nitromethane in the presence of mercuric salts, and by then removing the protecting groups by treatment with methanolic ammonia and hydrolysis with Dowex 1X2. The synthetic sample was shown to be identical with natural paromamine by a comparison of their infrared spectra and by microbiological assay. The identity was also proved by the determination of the Δ[M]Cu Am values of the tri-N-acetate of the synthetic and natural specimens by the copper-complex methods.
Sigma-Pi Interaction Accompanied by Stereoselection
Authors: Fukui Kenichi , Fujimoto Hiroshi
Published: July 2006

A simple molecular orbital theoretical treatment of the sigma-pi interaction caused by chemical reactions of planar-conjugated systems has been developed. The problem of the streo-selection of the two alternative directions of configuration altering due to the hybridization change at the centers of interaction has been considered by means of a simple perturbation treatment. Two theoretical indices, which represent the conjugation stabilization by way of the sigma-pi and reagent-pi interactions, have been introduced for this purpose. The theoretical results are consistent with the results of experience so far accumulated in various organic reactions, such as additions, eliminations, substitutions, and rearrangements, of conjugated molecules.
Dielectric Relaxation and Molecular Structure. III. Relaxation Times of Aniline Derivatives in Benzene and Dioxane
Authors: Chitoku Kazuo , Higasi Keniti
Published: July 2006

A brief description is made of the experimental methods for measuring microwave dielectric constants and losses of solutions in the frequency range 10–50 Gc./sec. Dielectric data obtained in this experiment were analysed from the viewpoint of molecular interaction between the solute and the solvent molecules. Six benzene derivatives with the amino group, aniline (A), N,N′-di-methylaniline (B), N,N′-diethylaniline (C), 2, 6-dimethylaniline (D), p-nitroaniline (E) and N-methylaniline (F) were chosen as solutes. Benzene and dioxane were used as solvents. The relaxation times of A, D and E obtained in dioxane are about three or five times larger than the corresponding relaxation times in benzene. The relaxation times of B and G in dioxane were about twice or one and half of the corresponding values obtained in benzene. The dielectric behavior of F is intermediate between A and B. These results are attributable to the hydrogen-bond formation between an oxygen atom of the dioxane molecule and an amino-hydrogen atom (F) or atoms (A, D and E).
The Separation of Zirconium and Hafnium by Tributyl Phosphate - Celite Reversed-phase Partition Chromatography
Authors: Ueno Kaoru , Hoshi Michio
Published: July 2006

The distribution ratios, Kd, for zirconium and hafnium were measured in the hydrochloric acid-TBP-celite system, the acid concentration being varied from 5 n to 8 n. The data obtained showed that the separation factor for the above elements, Kdzr⁄KdHf, is fairly high, –4, in the 7–8 n hydrochloric acid range. Thus, the separation of these elements was carried out in 7.1 n hydrochloric acid by the use of a TBP-celite column.
The Mechanism of the Alkaline Fusion of Diphenylsulfone
Authors: Oae Shigeru , Furukawa Naomichi
Published: July 2006

Diphenylsulfone-1-14C was treated with fused potassium hydroxide at 300°C for 7 hr. in a sealed metal tube. The yield of phenol, as determined by the isotope dilution technique, was found to be almost quantitative. The distribution of 14C in the resulting phenol was determined by degradating it by the usual method. Practically all the activity of 14C in the phenol was found at the position 1, which corresponded to the originally-labeled position in the diphenylsulfone-1-14C used. This indicates that the mechanism of the alkaline fusion of diphenylsulfone proceeds thruogh a simple SN2-type mechanism, not the elimination-addition mechanism.
Diffusion in Glassy Polymers. III. Temperature Dependence and Solvent Effects
Authors: Odani Hisashi , Kida Shigeru , Tamura Mikio
Published: July 2006

Absorption and desorption of benzene and ethyl acetate by atactic polystyrene (A-PS) were studied at various temperatures below the glass transition point of the polymer. In the A-PS+ benzene system raising temperature did not alter the general feature of the family of successive differential absorption curves, but merely compressed the whole family of curves towards a low concentration region. The critical concentration of penetrant at which the transition from non-Fickian to Fickian behavior occurred became lower in the order benzene, ethyl methyl ketone, and ethyl acetate. The logarithm of the time, t*, which specifies the inflection point of the second stage on the two-stage absorption curve, were linearly dependent on the initial concentration of penetrant, Ci, and the correlation lines between log t* and Ci obtained for various combinations of temperature and solvent were nearly parallel with one another. The features of integral absorptions were essentially the same in all cases, and the absorption curves showed a pronounced dependence on concentration.
The Photochemical Sulfoxidation of Alkylbenzenes
Authors: Ogata Yoshiro , Izawa Yasuji , Tsuda Takao , Takagi Katsuhiko
Published: July 2006

The photochemical sulfoxidation of alkylbenzenes with sulfur dioxide and oxygen in acetic anhydride to give the corresponding sulfonic acids has been studied. The sulfoxidation of the higher alkylbenzenes, such as that with a side-chain of trimerized propylene (ABTP) with a total average mol. wt. of 253 and that with a linear side-chain (ABL) with an average mol. wt. of 254, and also that of ethylbenzene give, by homolytic reaction, the corresponding sulfonic acids substituted at their side-chains. In contrast, the sulfonation of m-xylene occurs at the benzene ring by ionic reaction, while toluene gives a very poor yield of sulfonic acid. The surface activities of the resulting sodium alkylbenzenesulfonate with their sulfonate group at the side-chain were comparable to the corresponding ring-substituted sulfonates.
The Reaction of Optically Active Silver β-Phenylisobutyrate with Halogen
Authors: Oae Shigeru , Kashiwagi Teruya , Kozuka Seizi
Published: July 2006

The Hunsdiecker reaction of optically active silver β-phenylisobutyrate with bromine was carried out, and racemic β-phenylisopropyl bromide and optically atcive 3-methyl-7-bromo-hydrocoumarin were obtained as the major products. Meanwhile, the Simonini reaction was also performed with the same optically active acid and iodine; 1-phenyl-2-propyl β-phenylisobutyrate was obtained as the product here. Upon the hydrolysis of the ester, the resulting alcohol, β-phenylisopropyl alcohol, was found to be racemic. From these observations, the mechanisms involving the formation of the incipient free radical during the reactions were suggested for both the reactions.
Heptafulvenes. VI. The Structure of 2,3-Diamino-8,8-dicyanoheptafulvene Hydrochloride
Authors: Kato Tadahiro
Published: July 2006

2,3-Diamino and 2,3-bismethylamino-8,8-dicyanoheptafulvenes gave the corresponding crystalline salts of hydrochloride. From the infrared and ultraviolet spectra, it was concluded that these hydrochlorides are the derivatives of the hydrochloride of 2-aminotropoimine.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. II. The Effect of Catalyst and Water Concentrations of the Molecular Weight of the Polymer
Authors: Higashimura Toshinobu , Miki Tetsuro , Okamura Seizo
Published: July 2006

In the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2, the dependence of the molecular weight of the polymer formed on the polymerization conditions has been studied. In general, the molecular weight of the polymer formed increases in the course of polymerization, keeps a constant value over a certain range of conversion, and then again incerases remarkably. The molecular weight of the polymers formed decrease with an increase in the catalyst and water concentrations. This phenomenon can be explained qualitatively on the assumptions that the rate of the propagation reaction is smaller than that of the initiation reaction and that the chain breaking occurs through the reaction with water, which is consumed as the polymerization proceeds. This is equal to the assumption that the chain carrier is an oxonium ion in the cationic polymerization of trioxane.
The Analysis of Activators in Several Phosphors
Authors: Kotera Yoshihide , Sekine Tadao , Takahashi Masao
Published: July 2006

The activators in the zinc sulfide phosphors were analyzed by colorimetry. The reagents were p-dimethylaminobenzylidene-rhodanine for the determination of silver in zinc sulfide and sodium dithiocarbamate, and zinc dibenzyldithiocarbamate for copper. The analytical procedures were discussed, and the range of the activator content to which these procedures are applicable was clarified. The methods were then used to determine the activator contents in the phosphors in the form of powder and single crystals; the results obtained make it clear that the activators are dissipated during the firing process in the preparation of phosphors and that copper is incorporated during the single-crystal preparation.
Vibrational Spectra and Structure of Substituted Unsaturated Carbonyl Compounds. VI. β-Halogeno- and β-Halogenodeuteriovinyl Ketones
Authors: Dabrowski Janusz , Kamienska-Trela Krystyna
Published: July 2006

The infrared spectra of several chloro-, bromo- and iodovinyl ketones and their partly deuterated derivatives were investigated in the liquid state and in solutions. A Raman spectrum of one of these substances was also obtained. It has been shown that, unlike enamino- and hydroxyvinyl ketones, the title compounds exhibit fairly characteristic absorption bands due to carbonyl and skeletal vibrations. The splittings observed in the double bond stretching region are accounted for by rotational isomerism. Several assignments of the group frequencies are proposed.
Studies of the Quenching of the Fluorescence of Acridine Orange from the Standpoint of Charge-Transfer
Authors: Komiyama Tomoko , Miwa Takuji , Koizumi Masao
Published: July 2006

The quenching action of N, N-dimethylaniline, nitrobenzene, s-trinitrobenzene and tetracyano-ethylene on the fluorescence of acridine orange (AO) has been studied using ethanol and dioxane as solvents. In these solvents AO exists as cations or neutral molecules. In the former solvent, the quenching actions of the above substances on these two species have been investigated separately. The quenching constants, K’s (in reference to the Stern-Volmer equation) of the above substances (in the above sequence) in ethanol are (34–35), (19.6), (53.6) and (∼90) for cations and (8.4), (72.8), (−), and (−) for neutral molecules (in l./mol.). Thus, when quenchers are electron acceptors, K increases with the accepting power: nitrobenzene<s-trinitrobenzene<tetracyanoethylene. Further, acceptors are more efficient quenchers on neutral molecules than on cations (nitrobenzene), whereas the reverse is true for donors (N, N-dimethylaniline). In dioxane the quenching constants are generally somewhat smaller than in ethanol, but a basic similarity has been confirmed. All the results support the view that the present quenching phenomena are closely related to a charge-transfer process.
Studies of the Aqueous Solution of a Surface Active Substance by Means of an Ultrasonic Interferometer. III. Determinations of Ionic and Nonionic Hydrations of Sodium Alkyl Sulfate
Authors: Shigehara Koji
Published: July 2006

The amounts of water of ionic and nonionic hydration were calculated for sodium alkyl sulfate in the state of molecular dispersion from the data obtained by the author and under the assumptions usually adopted: (a) the solution, as a whole, consists of several volume elements of different compressibilities; (b) the ionic radical together with its hydration water is incompressible; (c) the compressibility of the water of nonionic hydration for the CH2 group of the hydrocarbon chain is the same as that of ordinary ice; (d) the compressibility and the molar volume of the CH2radical in the state of molecular dispersion are the same as those in the micellar state. The water of hydration was calculated to be 2.1 mole per mole of the CH2 radical, and 4.9 mole per mole of the ionic radical, the latter value being the same as that of the solute in the micellar state previously reported. The molar volume of the water of nonionic hydration is found to be slightly less than that of free water, in accordance with the prediction of others. The dehydration of sodium alkyl sulfate caused by the addition of inorganic electrolyte has also been observed.
Polarographic and Potentiometric Studies of Indium(III)- and Europium(III)-Iminodiacetate Complexes
Authors: Misumi Seizo , Aihara Makoto
Published: July 2006

The successive chelate formation constants for In(III)- and Eu(III)-IDA complexes were obtained by potentiometric titration and calculation by Bjerrum’s method. The values of logK1 and logK2 for the In(III)-IDA complex are 9.54 and 8.87, and those for the Eu(III)-IDA complex are 6.22 and 4.72, respectively. The electrode reactions of these complexes were studied polarographically and found to be irreversible and diffusion-controlled. The ionic states of these complexes before reduction in the vicinity of the electrode surface were estimated to be [InY2(OH)]2− or InY2− and Eu(H2O)x3+. The rate constant, (kf°)B, of the electron transfer for the Eu(III)-IDA complex was calculated to be 1.3×1020 cm.sec−1.