bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Reaction between Hydrocarbon and Hydrogen Cyanide in Silent Electrical Discharge. I. The Formation of Cyclohexyl Cyanide from Cyclohexane and Hydrogen Cyanide
Authors: Kawamoto Kazuaki , Sonoda Noboru , Tsutsumi Shigeru 
Published: July 2006

Abstract
In order to examine the possibility of the direct introduction of a cyano radical into cyclohexane by means of silent discharge, a mixture of cyclohexane and hydrogen cyanide was discharged in an ozonizer under various conditions. As a result, cyclohexyl cyanide was obtained. The yield of cyclohexyl cyanide depended upon the voltage of discharge, the residence time in the discharge tube, the temperature of the discharge tube, and the structual characteristics of the apparatus. In the refluxing method the maximum yield of cyclohexyl cyanide was obtained when the discharge was carried out at a low temperature. Besides cyclohexyl cyanide, the reaction products were confirmed to consist of bicyclohexyl, cyclohexene, methylcyclohexane, ethylcyclohexane, 3-cyclohexylcyclohexene, methylenecyclohexane, 1-hexene, n-hexane, n-pentane, methylcyclopentane, a solid brown deposit, and cracked gas. The principal reactions can be interpreted as being the formation of cyclohexyl and cyano radicals and the combination of these radicals, their dehydrogenation, their isomerization, their polymerization, and their decomposition.
Kinetic Studies of Solvolysis. XV. Racemization Caused by the Molecular-Complex Formation in the Acetolysis of Optically Active 2,4,7-Trinitro-9-fluorenyl (+)-Camphor-10-sulfonate
Authors: Okamoto Kunio , Nitta Issei , Shingu Haruo 
Published: July 2006

Abstract
Optically active 2,4,7-trinitro-9-fluorenyl (+)-camphor-10-sulfonate (II) has been synthesized by asymmetric attack of (+)-camphor-10-sulfonic acid to 9-diazo-2,4,7-trinitrofluorene. Acetolysis of II is accelerated by added phenanthrene, anthracene, and hexamethylbenzene at 116–120°C. This acceleration is attributed to molecular complex formation between II and these hydrocarbons. The complex formation has been examined by spectrophotometry or by the isolation of the crystalline complex of II. The acetolysis product, i.e., optically active 2,4,7-trinitro-9-fluorenyl acetate (III), has been racemized in the greater degree in the presence of the more aromatic hydrocarbons. This racemization is ascribed to the prolonged life of the Sn1 ion-pair intermediate caused by the rapid equilibration between the uncomplexed and the complexed Sn1-intermediate; the kinetic nature of this interaction has been discussed.
Azirines. III. The Preparation of Azirine Derivatives by the Base-Catalyzed Rearrangement of Quaternary Hydrazones
Authors: Sato Shimao 
Published: July 2006

Abstract
An attempt to prepare azirines by the base-catalyzed rearrangement of some quaternary hydrazones gave the corresponding azirine derivatives. Namely, 2-phenyl-3-methylazirine was obtained by the treatment of propiophenone dimethylhydrazone methiodide with potassium t-butoxide, but treatment with sodium isopropoxide gave 2,5-diphenyl-3,6-dimethylpyrazine or 2-phenyl-2-isopropoxy-3-methylaziridine, depending on the reaction conditions. 2-Phenyl-3,3-pentamethyleneazirine was obtained in a good yield by the treatment of cyclohexyl phenyl ketone dimethylhydrazone methiodide with sodium isopropoxide.
Investigation of Copper(II) Chelate with Chromotropic Acid
Authors: Wake Ryousuke , Miyata Haruo , Tôei Kyoji 
Published: July 2006

Abstract
Copper(II)-chelate with chromotropic acid was investigated by potentiometric titration. The measurement have been carried out at 25.0±0.1°C and μ=0.10 (with KNO3). The acid dissociation constant of chromotropic acid, the formation constant of the 1 : 1 chelate (the molar ratio of ligand to copper(II) ion) and th hydrolysis constant of this chelate were determined.
Reaction of Butadiene with Ethylene. IV. Synthesis of 1,4-Hexadiene by a Cobaltous Chloride-Ditertiary Phosphine Complex and an Organoaluminum Compound Catalyst
Authors: Iwamoto Masao , Yuguchi Sadao 
Published: July 2006

Abstract
A new catalyst consisting of a cobaltous chloride-ditertiary phosphine complex and an organoaluminum compound was found to be effective for the selective preparation of 1, 4-hexadiene by the reaction of butadiene with ethylene. The effects of the reaction variables on the activity and on the selectivity in 1, 4-hexadiene formation were studied. It is considered that a coordination of the ditertiary phosphine on the catalytically activated intermediate is essential for the selective catalysis. A reaction mechanism is proposed which involves an activated hydrido-cobalt complex as intermediate.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. IV. The Anion Radicals of Some Substituted Methyl Benzoates
Authors: Hirayama Masatoshi , Isobe Taro 
Published: July 2006

Abstract
ESR spectra are observed for the anion radicals of methyl p-, m- and o-nitrobenzoates, methyl ester of p-phthalaldehydic acid, and methyl and ethyl p-cyanobenzoates. Both the electrolytic and alkali-metal reduction methods are used for the radical generation. The spin densities calculated by McLachlan’s procedure only with the adjustment of the resonance-integral parameter for the ester group-ring bond are in good agreement with those obtained experimentally for most of the substituted positions in these radicals. The result for the methyl o-nitrobenzoate anion suggests that the ester group is twisted considerably by the large steric hindrance between the ester and nitro groups. The ring-proton splittings of three p-substituted methyl benzoate anions show that the known order of electron-withdrawing effects of the substituents, NO2&gt;CHO&gt;COCH3&gt;COOCH3&gt;CN, holds also for these anions. And it is suggested that the electron-withdrawing power of a XM+ group produced on the alkali-metal reduction increases in the order of free NO2, NO2Cs+,NO2K+,NO2Na+ and NO2Li+, and that the groups CHONa+ and CHOK+ are more electron-withdrawing than a free CHO group. The ring-proton splittings obtained from the VB-superposition calculations for all the anions except for the o-derivative are in satisfactory agreement with those from the MO calculations. Structural models of ion complexes are proposed for the p- and m-nitro derivatives and methyl ester of p-phthalaldehydic acid with the assistance of MO calculations.
Deuteron Magnetic Resonance of NiSiF6·6D2O and NiSnCl6·6D2O
Authors: Chiba Takehiko , Soda Gen 
Published: July 2006

Abstract
Deuteron magnetic resonance study was made on single crystals of NiSiF6·6D2O and NiSnCl6·6D2O. Deuteron quadrupole coupling tensors were determined at various temperatures. In NiSiF6·6D2O, the quadrupole coupling at −116°C is that of stationary D2O, at 23°C and at 70°C that of D2O under rapid 180°-flip motion and at 150°C that of rapid Ni(D2O)62+ reorientation. The eqQ⁄h values at −116°C, 238.3±1.3 kc and 235.7±1.9 kc do not appear to show marked effect of strong coordination. In NiSnCl6·6D2O, the quadrupole coupling corresponding to D2O under 180°-flip motion is observed at −53°C, at 25°C, and at 55°C. Spectra corresponding to a stationary D2O are not observed even at 77 °K. From the orientation of quadrupole tensors probable crystal structures of these compounds are proposed. Line width transitions were observed from which the reorientation rate was derived. The estimated activation energies of the 180°-flip motion of D2O are 7.6 and 4.3 kcal/mol in the fluosilicate and chlorostannate, respectively, and that of Ni(D2O)62+ reorientation in the fluosilicate is 19 kcal/mol. Additional measurements of 19F and 1H resonances indicate the setting in of the SiF62− reorientation at −110°–−120°C in NiSiF6·6H2O, and that of the Ni(H2O)62+ reorientation in the chlorostannate at approximately the same temperature as the fluosilicate.
The Diffusion of Gases at High Pressures. II. The Diffusion of 14CO2 in the 12CO2-Ar System
Authors: Takahashi Shinji 
Published: July 2006

Abstract
The diffusion coefficients of 14CO2 in argon and in binary mixtures of normal carbon dioxide and argon were measured at the temperatures of 25, 50 and 75°C in the 15—250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell using the radioactive tracer technique. The products of the binary diffusion coefficient of 14CO2 in argon and the density increase with an increase in the density. This tendency is not predicted by Enskog-Thorne’s mixed dense gas theory, which requires that the products decrease with an increase in the density. The products of the diffusion coefficient of 14CO2 in the mixtures and the density increase slightly with an increase in the density in the region of lower density at each temperature. However, in the region of higher density they decrease slightly at 25 and 50°C and are nearly constant at 75 °C. The values extrapolated to 1 atm agree fairly well with the experimental findings of Holsen et al. and those predicted by kinetic theory.
Liquidus Curve Measurements in the ZrO2-MgO System with the Solar Furnace
Authors: Noguchi Tetsuo , Mizuno Masao 
Published: July 2006

Abstract
A liquidus curve in the system ZrO2-MgO was investigated by the use of a heliostat type solar furnace. The cooling curves of a composition were obtained by the specular reflection method with a brightness pyrometer. Quenched specimens from the melt were examined with an X-ray technique and a petrographic microscope. Newly found anomalies on the liquidus curve were 7.5, 12.5 and 17.5 mol% MgO compositions. The composition of 12.5 mol% MgO quenched from the melt showed the new cubic-like phase of which optic angle of 2 V equals to −74°C and decomposed easily into monoclinic and tetragonal forms by reheating at 1300°C.
An Experimental Study on the Role of Water Vapor in the Distribution of Fluorine and Chlorine in Volcanic Rocks
Authors: Sugiura Tsutomu 
Published: July 2006

Abstract
Fluorine and chlorine contents of volcanic rocks were examined with respect to the characteristics of the rocks. Fluorine showed rather linear relationships with some chemical components of the rocks and also with stages in the differentiation of magmas. But any universal relationship covering all the rock types was not found. The cause of this fact is expected to be the loss of halogens from rocks resulted from the interaction between rocks and water vapor, which is believed to be ubiquitous in magma and is gradually emanated from it during or after the formation of rocks. So, in order to make clear the role of water vapor in the distribution of halogens in rocks, the author has distilled fluorine and chlorine from rock samples with water vapor at elevated temperatures and studied following relations; (1) the relationship between the amount of distilled halogens and the fluorine and chlorine contents of the rocks, and (2) the relationship between the amount of distilled halogens and the characteristics of the rocks. In distillation of fluorine and chlorine with water vapor, almost all fluorine remained in each rock specimen at low temperatures below 300°C, and at temperatures above 700°C the ratio of the amount of distilled fluorine to the initial amount of fluorine in rocks fluctuated among specimens. However, there was no relation between patterns of the distilled fluorine and the fluorine content of the rocks, and also the characteristics of the rocks. Meanwhile, distillation curve of chlorine showed various patterns without having any relation to chlorine content of the rocks, and indicated that chlorine was retained more in basic rocks than in acidic rocks at higher temperatures, although no relation was observed between the chlorine content of the rocks and the characteristics of the rocks. Generally the ratio of distilled fluorine to initial fluorine in rocks is smaller than the ratio of distilled chlorine to initial chlorine in rocks at low temperatures. The results of the distillation experiments suggest that the distillation process of halogens with water vapor controlls the distribution of halogens in volcanic rocks more than does the chemical and mineralogical nature of the rocks.
Short-Lived Nuclides Formed by (γ, n) Reactions with 20MeV Bremsstrahlung
Authors: Oka Yoshinaga , Kato Toyoaki , Yamadera Akira 
Published: July 2006

Abstract
The most prominent (γ, n) reaction products with half-lives from 10 sec to about 1 min formed by irradiation of some 7 elements with 20 MeV bremsstrahlung have been determined in order to study the applicability of these products to photoactivation analyses. Irradiation was carried out for 1 min with 20 MeV bremsstrahlung radiation with a dose rate of 107 R/min. The reactions investigated are 24Mg(γ, n)23Mg, 76Ge(γ, n)75mGe, 78Se(γ, n)77mSe, 92Mo(γ, n)91mMo, 140Ce(γ, n)139mCe, 142Nd(γ, n)141mNd and 159Tb(γ, n)158mTb. The yields of these reactions have also been obtained through the absolute measurement of resultant activities. The isomeric yield ratios have been discussed on the basis of the nuclear properties of the residual nuclides. The observed ratios generally favor the isomer whose spin is closer to that of the target nucleus. For the elements studied, the lower limits of detection averaged about 1 μg under present experimental conditions.
A New Synthesis of Pyridoxal-5-phosphate
Authors: Iwanami Masaru , Numata Toshiko , Murakami Masuo 
Published: July 2006

Abstract
By the hydrolysis of pyridoxal-5-phosphate Schiff bases, pyridoxal-5-phosphate was prepared in a crystalline form without any further purification. Pyridoxal-5-phosphate Schiff bases were prepared in good yields by the phosphorylation of pyridoxal Scruff bases and were easily purified by alkali-acid reprecipitation. The pyridoxal-5-phosphate thus obtained was demonstrated to be identical with an authentic sample by a study of its UV, IR, and NMR spectra.
Kinetics of the Aquation of Pentammine Amino Acid Cobalt(III) Complexes
Authors: Ogino Kazuko , Murakami Tasuku , Saito Kazuo 
Published: July 2006

Abstract
The rate of aquation of pentamminecobalt(III) complexes of the general formula [Co(NH3)5amH]3+ (amH stands for an amino acid molecule with proton on the nitrogen atom), containing unidentate glycine, β-alanine, sarcosine and betaine, has been measured at 55°C, and ionic strength 0.1 and 1.0 in the acid concentration range up to 0.5 m. The kinetic term is expressed by
Rate=[complex](k_H_2O+k_H^+[H^+])
The kH2O and kH+ values for glycine, β-alanine, sarcosine and betaine complex are respectively as follows (at μ=1.0): kH2O, 0.40×10−6, \lesssim0.2×10−6, 0.25×10−6, and 0.44×10−6 sec−1; kH+, 2.0×10−6, 26×10−6, 1.8×10−5, and 1.0×10−6 m−1 sec−1. The kH+ alues increase with increase in pKa values of the amino acids, but are smaller than those for the aquation of carboxyl-atopentamminecobalt(III) complexes. This difference seems to be due to the electrostatic shielding of the car boxy late group by the protonated amino group.
The Cyclization of Ethyl Acetoacetate and Ketones by Ammonium Acetate
Authors: Sakurai Akio , Midorikawa Hiroshi 
Published: July 2006

Abstract
The reactions of ethyl acetoacetate with cyclic ketones and aromatic methyl ketones by using excessive ammonium acetate gave some heterocyclic compounds, such as 2-hydroxy-4-methyl-5, 6, 7, 8-tetrahydroquinoline (III), 2-hydroxy-4-methyl-6, 7-dihydro-5H-1-pyrindine (IV), and 2-hydroxy-4-methyl-6-alkyl-pyridines (VI). The structures of these compounds were investigated by means of their infrared and NMR spectra.
Studies of the N-Oxides of N,N-Dialkylainino Acids. I. The Syntheses of N,N-Dimethyl Neutral Amino Acids and Corresponding N-Oxides
Authors: Ikutani Yoshikazu 
Published: July 2006

Abstract
The N,N-dimethyl derivatives of neutral amino acids, such as glycine. l-alanine, Dl-alanine, l-valine, Dl-valine, l-leucine, l-phenylalanine, and l-tyrosine, were prepared by the catalytic reductive condensation of the corresponding amino acids with formaldehyde. The N-oxides were satisfactorily synthesized by the oxidation of the N,N-dimethyl derivatives with an aqueous mixture of hydrogen peroxide and acetic acid. The reaction conditions, the analytical data, and some properties of the products are presented.
Stability of Hydrosol of Arsenic Trisulphide in the Light of D. L. V. O. Theory
Authors: Daluja K L , Srivastava S N 
Published: July 2006

Abstract
The stability of negative As2S3 sol of mean particle diameter 90 Å has been studied in presence of different valent cations viz. Na+, Ba2+, UO22+, Al3+ and Th4+ using D. L. V. O. theory. The zeta potential (assumed to be equal to the surface potential) of the sol particles was calculated from the electrophoretic measurements as a function of ionic strength. The knowledge of zeta potential permitted the calculation of repulsive energy VR, and the energy of attraction VA was estimated from physico-chemical data. The stability ratio, W was calculated from interaction profiles which were made from the combination of the two energies. Stability factor, F, was also estimated from the Derjaguin equation, but it was not satisfactory presumably owing to the exclusion of VA. In general, the interaction between As2S3 particles could be interpreted in the light of D. L. V. O. theory. The flocculation powers of cations were in the order of Al3+&gt;Th4+&gt;UO2+&gt;Ba2+&gt;Na+. The anomalous behaviour of thorium is perhaps due to its hydrolysis.
The Wolff Rearrangement. IV. The Silver-salt Catalyzed Decomposition of α-Diazoacetophenones in Benzene Solution
Authors: Takebayashi Matsuji , Ibata Toshikazu 
Published: July 2006

Abstract
The decomposition of α-diazoacetophenone (I) in benzene solution has been studied using a silver benzoate-triethylamine catalyst at 50°C in an atmosphere of nitrogen. The reaction gave 3-benzoyl-4-hydroxy-5-phenylpyrazole (II) and β-phenylpropiophenone (III). In the decomposition of the substituted compounds, such as p-methoxy-, p-methyl- and p-nitro-α-diazoacetophenones, the corresponding substituent products of II and III were also obtained. The formation of II and III is reasonably explained by assuming two kinds of reactions between phenylketene and I.
Photochemischer Zerfall von Benzoylphenylacetyl- und Benzoyl-p-chlorphenylacetyl-peroxyden in Toluol
Authors: Suehiro Tadashi , Hibino Shuji , Saito Tadashi 
Published: July 2006

Abstract
Benzoylphenylacetylperoxyd und Benzoyl-p-chlorphenylacetylperoxyd zerfallen photolytisch in Toluol bei −5–−10°C in die Benzoyloxy und Benzyl bzw. p-Chlorbenzyl Radikale unter Bildung von Kohlendioxyd, Benzoesäure, Benzoesäure-benzyl- bzw. -p-chlorbenzyl-ester, Bibenzyle, Methyldiphenylmethane, Diphenylmethane und Methyldiphenyle. Eine Umlagerungsreaktion vom Peroxyd in den Benzylkohlensaurebenzoesäureanhydrid verläuft nebenbei und dieser Anhydrid liefert durch Einwirkung auf Benzoesaure, Kohlendioxyd, Benzylalkohol und Benzoesäureanhydrid. Die freie Radikale Reaktion und die Umlagerung in den Kohlensäureanhydrid vom Peroxyd finden im Verhältnis ca. 2:1 statt. Aus dem Lösungsmittel, Toluol, entsteht Benzyl Radikale wahrend der Photolyse durch Einwirkung von Benzoyloxy Radikal, dies wurde durch das Vorkommen von Bibenzyl und p-Chlorbibenzyl bei der Photolyse von Benzoyl-p-chlorphenylacetylperoxyd in Toluol nachgewiesen.
Magnesium Ammonium Phosphates, Related Salts and Their Behavior in Compound Fertilizers
Authors: Ando Jumpei , Akiyama Takashi , Morita Matsusaburo 
Published: July 2006

Abstract
Fluorine forms a previously unknown compound MgNH4HFPO4 (MAFP) when monoammonium phosphate made from wet-process phosphoric acid is treated with magnesium hydroxide above about 75°C in the presence of moisture. When treatment is conducted with a large quantity of water, fluorine forms a gelatinous material which resembles MAFP in chemical composition. Wet-process phosphoric acid ammoniated and reacted with magnesium hydroxide above about 75°C gives a very thick slurry, which almost solidifies due to the formation of gelatinous material, while the acid treated in the same way after being defluorinated gives a less viscous slurry in which most of the magnesium is present in the form of MgNH4PO4·H2O (MH). Fluorine shows less effect at lower temperature. When treated below about 60°C, most of the magnesium combines to form MgNH4PO4·6H2O (M6H) and Mg(NH4)2(HPO4)2·4H2O (M4H). M6H and M4H decompose during drying at about 100°C, losing ammonia and water of crystallization to form amorphous materials. The decomposition is promoted by the presence of potassium salts resulting in the formation of water-insoluble potassium. Another previously unknown compound, MgKHFPO4 (MKFP), which is isomorphic with MAFP has also been identified. MKFP is less soluble in water while MAFP decomposes in water to precipitate amorphous material and M6H. Solid solutions of MAFP and MKFP are often present in commercial fertilizers, and provide a small amount of water-insoluble potassium. M4H decomposes rapidly in water to precipitate M6H. M6H and MH are less soluble in pure water but are considerably soluble in water which contains acidic salts, such as monoammonium phosphate.
Phase Transitions and Thermodynamic Properties of Rubidium and Cesium Cyanides
Authors: Sugisaki Masayasu , Matsuo Takasuke , Suga Hiroshi , Seki Syûzô 
Published: July 2006

Abstract
Heat-capacity measurements were performed for rubidium and cesium cyanide crystals between 15 and 300°K. It is found that each crystal has only one anomalous peak in its heat capacity curve, being located at 110.3°K and 193.1°K for rubidium and cesium cyanides, respectively. By the comparison of the present data with those for potassium and sodium cyanides, it was shown that these anomalous heat capacities can be interpreted in terms of the orientational ordering processes of cyanide ions in the crystals. It was suggested that there should exist the residual entropy due to the frozen-in state in their orientational configuration and they were estimated as Rln4 for rubidium cyanide and Rln2 for cesium cyanide.
Intramolecular Interaction between Hydroxyl Group and Carbonyl Moiety in Keto-alcohols
Authors: Oki Michinori , Iwamura Hiizu , Aihara Jun-ichi , Iida Hiroshi 
Published: July 2006

Abstract
The O–H stretching absorption (νO–H) spectra of some keto-alcohols have been examined. The νO–H shift to the lower frequency due to the intramolecular O–H··· bonding can roughly be correlated to the geometry of the hydroxyl group relative to the n-electrons on the carbonyl oxygen. When the bonding is forbidden because of the conformational restriction, a weaker interaction between the hydroxyl group and the π-electrons on the carbonyl group is observable as the lower shift of the νO–H by 10–30 cm−1 as far as the conformation is favorable for the interaction.
Kinetic Studies of Ammonia Oxidation in Shock Waves. IV. Comparison of Induction Periods for the Ignition of NH3-O2-N2 with Those for NH3-O2-Ar Mixtures
Authors: Miyama Hajime 
Published: July 2006

Abstract
Induction periods for ammonia oxidation in the NH3-O2-Ar and NH3-O2-N2 mixtures were measured by monitoring an ultraviolet absorption of ammonia in reflected shock waves. For the NH3-O2-Ar mixtures, induction periods in the temperature range of 1450–2730°K were found to be expressed by
logτ_i[O_2](mol·l^-1μsec)=-(16.24±0.17)+(10080±320)/T
when oxygen content is in the range of 4–10%, and by
long τ_i(μsec)=-(2.55±0.14)+(8810±220)/T
when the oxygen content is less than 1%. Values of induction periods for the 0.5% NH3-0.5%O2-99%N2 and 1% NH3-1%O2-98%N2 mixtures were also measured and compared with those for the NH3-O2 mixtures highly diluted with argon. Both results agreed well by taking into account vibrational relaxation of the reacting system if appropriate values of vibrational relaxation times for N2 dilute in NH3 is assumed. Therefore, possibility of coupling of vibrational relaxation of N2 and oxidation reaction was considered to be small.