bluuebunny/crossref_metadata_2025_split huggingface dataset:
Metal(II) Complexes of Ethylenediaminemonoacetic Acid (EDMA). Polarographic Studies of Cadmium(II) and Lead(II)-EDMA Complexes
Authors: Fujii Yuki , Ueda Teiko , Kodama Mutsuo 
Published: July 2006

Abstract
In the present paper, the d.c. polarographic behavior of cadmium(II) and lead(II) ions in ethylenediaminemonoacetate (EDMA) solutions was studied systematically. Since these metal(II) ions in an EDMA solution behave reversibly in a polarographic electrolysis, the compositions and the stability constants of cadmium(II)- and lead(II)-EDMA complexes could be estimated successfully from the shift of the half-wave potential of these metal(II) ions due to the complex formation with EDMA. The cadmium (II) ion was found to form complexes of 1-to-1 and 1-to-2 compositions with EDMA, and the electrode reaction mechanism was established to be:
(Remark: Graphics omitted.)
The successive formation constants of cadmium(II)-EDMA complexes, (K1)cdx and (K2)cdx were determined to be 3.01×108 and 5.65×104 respectively. On the other hand, the lead(II) ion forms only one complex with 1-to-l composition. In the presence of the chloride ion, the lead(II) ion was found to form a mixed ligand complex involving the chloride ion as well as a normal complex, PbX+, and the electrode reaction could be formulated as:
(Remark: Graphics omitted.)
The equilibrium constants, (K1)Pbx(=[PbX+]/([Pb2+]·[[X−])) and KpbxCl(=[PbXCl0]/([PbX+]·[Cl−])), were determined to be 1.69×108 and 1.01×10 respectively. The effect of the zinc(II) ion on the half-wave potential of the cadmium(II) ion in an EDMA solution was also studied. From the positive shift of the half-wave potential due to the presence of the zinc(II) ion, the formation constant of the zinc(II)-EDMA complex with a 1-to-1 composition was estimated to be 1.58×108.
The Stereochemistry of Hydrogenation and Hydrogenolysis. XI. The Stereochemistry of the Reduction of 3-Methyl-4-chromanone
Authors: Hanaya Kaoru 
Published: July 2006

Abstract
3-Methyl-4-chromanone (VIII) was reduced with a metal hydride complex, by the Meerwein-Ponndorf method and by catalytic hydrogenation. When VIII was reduced with a metal hydride complex and the Meerwein-Ponndorf method, trans-3-methyl-4-chromanol (IX) was produced as the main product. In the catalytic hydrogenation, VIII gave a cis-3-methyl-4-chromanol (X) as the main product over Raney nickel, but over the palladium catalyst the trnas isomer was larger than the cis isomer. These results indicate that, on Meerwein-Ponndorf and metal hydride reductions, the more stable product was formed as the main product; in the catalytic hydrogenation over the Raney nickel catalyst, VIII seems to be adsorbed mainly on the opposite side of the methyl group of the C-3 position and is hydrogenated to give the cis isomer, whereas, over the palladium catalyst, hydrogenation seems to proceed under the effect of “product development control over the catalyst” and the trans isomer is produced in a high yield.
Hammett Correlation in Mass Spectra. Substituent Effects for the Migratory Aptitude of the Aryl Group in the Unimolecular Ion Decomposition of Diaryl Sulfones
Authors: Nagai Toshikazu , Maeno Tetsuo , Tokura Niichiro 
Published: July 2006

Abstract
The migratory aptitude of the aryl group in the unimolecular ion decomposition reaction of p-substituted diaryl sulfones has been examined. Both electron-donating and -withdrawing substituents showed to be capable of increasing the migratory aptitude. On the other hand, a kinetic treatment allowed a satisfactory Hammett correlation (ρ=0.3) on the total abundances of the fragment ions. The energy of the cleaved bond and the production stability were shown to be important factors in the effect of the substituent on the ion decomposition.
Chemical Reactivity of Adamantane and Related Compounds
Authors: Fujimoto Hiroshi , Kitagawa Yoshihiko , Hao Hideyuki , Fukui Kenichi 
Published: July 2006

Abstract
The chemical reactivity of hydrogens in adamantane and substituted adamantanes has been calculated. The results of calculation have shown that the bridgehead hydrogens are most reactive toward electrophilic reagents or radicals. The chemical reactivity of hydrogens in diamantane, triamantane, and tetramantane has also been predicted. A discussion has been made of the stable configuration of the 1-adamantyl cation, radical, and anion and of the nature of the back-side conjugation between the two tertiary carbons in these species. A mode of the electrocyclic polymerization of p-quinodimethane to form polyamantane has been predicted on the basis of the symmetry properties of the frontier orbitals in the pi and sigma parts of p-quinodimethane.
Studies on Aminosugars. XXIV. The Facile Elimination of the Derivatives of a Pyranosid-4-ulose
Authors: Tsuchiya Tsutomu , Suo Kiyohiko , Umezawa Sumio 
Published: July 2006

Abstract
Methyl 3-azido-3-deoxy-α and β-d-xylopyranoside are prepared. The oxidation of the 2-O-benzoylated derivative of the above-mentioned α-anomer with the Pfitzner-Moffatt reagent leads to the facile elimination of the elements of benzoic acid and the formation of the 4-azido derivative of 5,6-dihydro-α-pyran-5-one. The 3-ethoxycarbonylamido derivative obtained from the above mentioned 3-azido derivative is oxidized similarly to afford the 4-ethoxycarbonylamido derivative of 5,6-dihydro-α-pyran-5-one. The mechanisms of these elimination reactions are discussed.
Kinetics and Mechanism of the Silver Catalysed Oxidation of Malic Acid by Potassium Peroxydisulphate
Authors: Agrawal G L , Bhattacharya Arun K 
Published: July 2006

Abstract
Preliminary experiments showed that the reaction between malic acid and potassium peroxydisulphate is very slow. The reaction rate becomes a measurable value at 25°C by introducing the Ag+ ion as a catalyst. The total order of the reaction has been found to be nearly unity. The effect of the concentration of catalyst and malic acid has been studied. The temperature coefficient of the reaction between the temperature range of 30 and 45°C is 1.76 and the mean value of the energy of activation is 10.9 kcal. The frequency factor and entropy of activation are 16.8×105 sec−1 and −41.1 e.u. respectively. The probable mechanism for the reaction has been suggested.
n-π* Electronic Emission Spectrum of o-Methoxybenzaldehyde Vapour
Authors: Srivastava M P , Singh O N , Singh I S 
Published: July 2006

Abstract
The n-π* vapour emission spectrum of o-methoxybenzaldehyde has been excited in transformer discharge in flowing vapours of benzene and the substance. In the spectrum the C=O stretching frequency is the most prominent and its found to form progression of bands. The entire spectrum has been analyzed in terms of several ground state frequencies.
Comparison of the Recoil Reactions in the 80mBr-CH4 and 82mBr-CH4 Systems
Authors: Tachikawa Enzo 
Published: July 2006

Abstract
The reactions of 80Br and 82Br excited by the isomeric transition processes with CH4 have been compared with each other. Similar reaction processes; energetic and thermal ionic, are involved in both cases. However, the isotope effect appears in the energetic process to form CH3Br, but not in the thermal ionic process to form CH3Br and CH2Br2. The difference in the γ-transitions of 80mBr and 82mBr to the ground states is responsible for the above results. It is concluded that at least a part of the recoil Br atoms enter chemical combinations with surrounding molecules within 10−8sec, the life-time of the excited 80Br atom. Furthermore, the yield of CH380Br, lower than that of CH382Br, is discussed on the basis of the different kinetic energies achieved on the Br atoms.
Thinning of Nonionic Detergent Films
Authors: Yamanaka Teruko 
Published: July 2006

Abstract
The effect of added electrolytes on the thinning of single vertical film formed from nonionic detergent solution has been studied. Addition of the electrolytes did not show an appreciable effect on the thinning of the film in the region of interference fringes. Specific effects of anions upon the “blackening time” (the time necessary for turning the total film area completely into a black film) were observed similarly to those on the cloud point. The order of magnitude of these effects followed the lyotropic series, which may be explained qualitatively by the effects on the dehydration of detergent molecules and on the electrical double layer of the film. The effect of the electrolytes on aqueous ionic detergent film was also examined. It was mainly explained by their influence on the electrical double layer.
Kinetics of Alkaline Hydrolysis of Esters. II. Unsaturated Esters and Oxalic Esters
Authors: Sharma R C , Sharma M M 
Published: July 2006

Abstract
The kinetics of alkaline hydrolysis of some typical esters, with unsaturation in the alkyl and the acyl portions, was studied. It was found that, in general, unsaturation results in enhancing the rate as compared to that of the corresponding saturated esters, provided that there is no conjugation between the double bond and the carboxyl carbonyl group. Oxalic esters hydrolyze relatively very fast due to the close proximity of the two ester groups. Rate constants for the alkaline hydrolysis of di-n-propyl-, di-isopropyl-, di-n-butyl-, di-s-butyl-, dicyclohexyl- and di-β-chloroethyl oxalates were obtained by using the theory of mass transfer accompanied by fast pseudo first-order reaction (diffusion method).
Far-Infrared Spectra and Lattice Vibrations of Barium Chloride Dihydrate
Authors: Fukushima Kunio , Kataiwa Hiroaki 
Published: July 2006

Abstract
The far-infrared spectra of barium chloride dihydrate and its deutero analog were measured in the region of 60–4000 cm−1. The assignment of the infrared bands due to crystal water and crystal heavy water was made on the basis of the band frequency shift associated with deuteration. The optically-active lattice vibrations were calculated in order to assign the far-infrared bands and elucidate the nature of the vibrations.
Microwave Spectra of o-Difluorobenzene in the Excited Vibrational States
Authors: Hatta Aritada , Kozima Kunio 
Published: July 2006

Abstract
The microwave spectra of o-difluorobenzene in various excited vibrational states have been measured in the frequency region from 10- to 30-GHz. The R- and Q-branch transitions of the a-type have been assigned. The rotational constants for the ν1=1 state are A=3254.77, B=2226.85, and C=1324.67 MHz, and those for the ν2=1 state are A=3269.76, B=2220.48, and C=1322.94 MHz. The inertial defects in the excited states have been used in order to make vibrational assignments. It is very probable that the ν1 and the ν2 mode are the out-of-plane vibration of A2 and the in-plane vibration of A1 respectively.
The Crystal Structure of Copper Yunainate Trihydrate, Cu(C5H8O3NS)2·3H2O
Authors: Furusaki Akio , Tomiie Yujiro 
Published: July 2006

Abstract
The crystal structure of copper yunainate trihydrate, Cu(C5H8O3NS)2·3H2O, has been studied by means of three-dimensional X-ray analysis. The crystal is monoclinic, with two formula units in a unit cell of the dimensions: a=15.94, b=6.33, c=8.60 Å, and β=95.6°; the space group is P21. The intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKα radiation around the b and c axes. The structure was elucidated by Sim’s method, and refined by the block-diagonal-matrix least-squares method, assuming anisotropic thermal motions for all the atoms. The final R factor is 9.2%. The copper atom is coordinated by imino nitrogen and carboxyl oxygen atoms of two yunainate groups, and a water oxygen atom. The first four atoms lie almost on a plane and make a square configuration of the trans type. The last one is bonded to the copper atom nearly in the direction of the normal of the plane. Thus, the coordination number of copper is five in the present crystal. Of the three sorts of water of crystallization, one is connected with the copper atom, as has already been mentioned, and the remaining two are lattice water, forming a hydrogen-bonded spiral chain around the screw axis. Further, these water molecules connect complex molecules to one another by their hydrogen bonds, forming a threedimensional hydrogen-bonded structure.
Kinetics of the Ligand Substitution Reaction of the Cobalt(II)-(Ethylene glycol)bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetate Complex with 4-(2-Pyridylazo)resorcinol
Authors: Funahashi Shigenobu , Tanaka Motoharu 
Published: July 2006

Abstract
The kinetics of the ligand substitution reaction of the cobalt(II)-(ethylene glycol)bis(2-aminoethylether)-N,N,N′,N′-tetraacetate complex (Co(II)-EGTA) with4-(2-pyridylazo)resorcinol (PAR) have been studied photometrically in the pH range 8–9.4 at an ionic strength of 0.1 and at 25°C. The reaction proceeds simultaneously through two different reaction paths. Thus the rate law can be written as
\fracd[CoR_2^-]dt=k_1[CoY^2-][HR^-]+k_2[CoHY^-][HR^-]
where Y4− and R2− refer to tetravalent EGTA and divalent PAR respectively. Rate constants, k1 and k2 are 3.2m−1sec−1 and 2.1×104m−1sec−1. Possible mechanism for the substitution is discussed. The stability constants for mercury(II)-EGTA complexes and cobalt(II)-EGTA complexes are determined by the mercury electrode method at μ=0.1 and 25°C in order to analyze the substitution reaction: KHgY=1023.86±0.10, kHgHYH=103.06±0.10, KCoY=1012.3±0.1, KcoHyH=104.9±0.1, KCoH2YH=103.3±0.3.
Absorption Spectra of 2E States of Some Chromium(III) Complexes Revealed by Flash Method
Authors: Ohno Takeshi , Kato Shunji 
Published: July 2006

Abstract
Excited states of some chromium(III) complexes were studied by a flash technique at −196°C. Transient species with strong absorption bands in visible and near UV regions were observed to decay at the same rate as their phosphorescence for CrIII(acac)3, K3[CrIII(NCS)6], NH4[CrIII-(NCS)4(NH3)2], and CrIII(exan)3. They are therefore 2E states (phosphorescent states). A strong absorption band for CrIII(acac)3 is assigned to a charge transfer transition from 2E state based on the intensity and energy of the transition. A transition to localized excited states in ligand with a small extinction coefficient was observed in near infrared region for CrIII(acac)3.
Macro Chelate Rings. II. Syntheses and Properties of 2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)xanthone as a Quadridentate Chelating Agent and Its Metal Complexes
Authors: Okawa Hisashi , Yoshino Tamotsu 
Published: July 2006

Abstract
2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)xanthone, a new quadridentate chelating agent, was synthesized by a sequence of steps and subsequently characterized. Some divalent metal complexes of the ligand were isolated, and their properties were characterized on the basis of infrared spectra. The non-coplanar structure of the complex derived from the ligand was suggested by the resolution of a cobalt(II) complex into optical isomers.
Syntheses of Benzodiazepine Derivatives
Authors: Motoki Shinichi , Urakawa Chikahiro , Kano Akio , Fushimi Yukio , Hirano T\={o}ru , Murata Katsumi 
Published: July 2006

Abstract
This communication deals with the syntheses of the aza-analogues of benzoheptafulvene. Acetylacetone or benzoylacetone reacted with benzophenone chloride in the presence of sodium ethoxide to form 3-(α-phenylbenzylidene)pentane-2,4-dione (XIVa) or 1-phenyl-2-(α-phenylbenzylidene) butane-1,3-dione (XIVc) respectively. Treatment of o-phenylenediamine with XIVa in acetic acid - ethanol resulted in forming 2,4-dimethyl-3-(α-phenylbenzylidene)-3H-benzo[b]-1,5-diazepine (XVa) which has a 3,6-diaza-4,5-benzoheptafulvene ring skeleton. Similarly, substituted o-phenylenediamines reacted with XIVa to give 7-substituted 2,4-dimethyl-3-(α-phenylbenzylidene)-3H-benzo[b]-1,5-diazepines (XVb)—(XVd). Reaction of XIVa with hydrazine gave only the monohydrazone of XlVa. The ketene dimer reacted with o-phenylenediamines to give 4-methyl-2,3-dihydro-2-oxo-1H-benzo[b]-1,5-diazepines (Xa)—(Xc). However, the condensation of Xa with aldehyde gave an undesirable product.
Effects of Additives on the Alternating Copolymerization of Aziridines with Cyclic Imides
Authors: Kagiya Tsutomu , Adachi Teruho 
Published: July 2006

Abstract
The effect of the addition of 2-methyl-2-oxazoline, which is an isomer of the growing chain end, was examined. The rate of the copolymerization of ethylenimine with succinimide increased upon the addition of 2-methyl-2-oxazoline. On the basis of this result and of the NMR spectrum of the copolymer, the mechanism of propagation via an activated state similar to oxazoline was proposed. The copolymerization was accelerated by the addition of sodium iodide, which is the catalyst of the isomerization of the growing chain end. The property of the copolymer obtained was different from that of the copolymer obtained without sodium iodide. Sodium iodide also affected the copolymerization of N-ethylethylenimine with succinimide, while it did not affect that of ethylenimine with N-ethylsuccinimide. The reduced viscosity of the copolymer increased with the reaction time. The reaction mechanism of the copolymerization in the presence of the catalyst was discussed on the basis of the facts mentioned above.
Spiro Compound Formation. IV. Acid-catalyzed Reactions of 2-Cyclohexylidenecyclohexanone Oxide
Authors: Nojima Masatomo , Hinoue Keniti , Tokura Niichiro 
Published: July 2006

Abstract
The reactions of 2-cyclohexylidenecyclohexanone oxide in the presence of (i) sulfuric acid, (ii) fluorosulfonic acid, (iii) boron trifluoride etherate, and (iv) antimony pentachloride have been studied. The products consisted of spiro[5.6]dodecane-7,12-dione, 2-(1-cyclohexenyl)-2-hydroxycyclohexanone, and 1,2,3,4,6,7,8,9-octahydrodibenzofuran. The ratio of the products was found to depend on the differences in the catalysts and solvents.
β-Ferrocenyl-α,β-unsaturated Ketones. II. The Reduction of β-Ferrocenyl-α,β-unsaturated Ketones and Their Relative Reactivities
Authors: Kono Hiromichi , Ishige Masayoshi , Sakai Koji , Shiga Mikio , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
The catalytic reduction of several β-ferrocenyl-α,β-unsaturated ketones was investigated using Urushibara nickel A (U-Ni-A) or precipitated nickel (ppt-Ni) as the catalyst, and their relative reactivities toward the catalytic reduction were discussed in comparison with those of the phenyl analogs. Some anomalies observed in the NMR spectra of the reduction products was also discussed.
Studies of Diazosulfides. I. A Kinetic Study of the Reaction of Diaryldiazosulfides with β-Naphthol in Alkaline Ethanol
Authors: Yamada Takashi , Tanaka Nobuo , Morisawa Takao , Nishikuri Masao , Kaji Aritsune 
Published: July 2006

Abstract
It was found that diaryldiazosulfides (I) reacted at an appreciable rate with β-naphthol in alkaline ethanol to produce azo-dyes. This is contrary to Hantzsch’s observation. The initialrate constants of the reaction were determined at various temperatures. The electron-donating substituents accelerated the rate when they were in the N-aryl part of I (substituent X) but retarded when in the S-aryl part of I (substituent Y). A set of ρ-values which have opposite signs, ρx=−2.96 and ρY=3.93, suggested that the rate-determining step in this reaction is the heterolytic rupture of the N-S bond of I. This was supported by the negative values of the entropy of activation and by such a solvent effect as that the rate was significantly increased when the polarity of the solvent increased. As the change in the concentration of β-naphthol affected the rate, the possibility of the participation of the transition state or of the intermediate including β-naphthol was also discussed.
Hydrogenation and Hydrogenolysis. XII. The Hydrogenation of Isomeric Dimethoxybenzenes with Platinum Metal Catalysts
Authors: Takagi Yuzuru , Ishii Sadayoshi , Nishimura Shigeo 
Published: July 2006

Abstract
The catalytic hydrogenation and hydrogenolysis of isomeric dimethoxybenzenes over six platinum metals have been investigated at elevated temperature and pressure. The hydrogenolysis of methoxyl group occurred more extensively over Group VIII3 metals than over Group VIII2metals. The meta isomer hydrogenolyzed to greater extent and gave smaller cis/trans ratio of dimethoxycyclohexane, than the ortho and para isomers. The greater tendency of the meta isomer toward hydrogenolysis supports the previously proposed explanation according to which the electron-releasing group at meta position would promote hydrogenolysis.
Activity Coefficient of Sodium in Dilute Sodium and Gold Alloy at 1400°K
Authors: Hirota Kazushi , Katsura Takashi 
Published: July 2006

Abstract
The equilibria between the molten Na2CO3 and the Au-Na alloys were determined at 1400°K under CO+CO2 gaseous mixtures. The activity coefficient of Na in the Au-Na alloys was constantly 0.0392±0.0028 at concentrations ranging from 0.2 to 0.02 wt% Na.
Statistical Thermodynamics of Binary Liquid Mixtures
Authors: Arakawa Kiyoshi , Kiyohara Osamu 
Published: July 2006

Abstract
By means of the cell method and using the Sutherland type potential function for pair interactions between molecules, a statistical theory was formulated for binary liquid mixtures consisting of rigid spherical molecules differing in size. A formula was derived for cohesive energy as a function of the volume of liquid, and studied in combination with the radial distribution function. The applicability of the square-well type potential function within a cell was also examined. Formulas for excess thermodynamic functions were derived and their applicability investigated. For 22 binary systems consisting of nearly spherical molecules, excess thermodynamic functions were calculated and compared with data in literature. The results show that the theory is applicable to the mixtures.
The Crystal Structure of Quinolinium 2-Dicyanomethylene-1,1,3,3-tetracyanopropanediide, [2(C9NH8)+·(C10N6)2−]
Authors: Sakanoue Seiki , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao 
Published: July 2006

Abstract
[2(C9NH8)+·(C10N6)2−] crystallizes in the form of the space group of Pbcn, with four formula units in the unit cell, and the following unit-cell dimensions: a=13.18, b=15.40, and c=11.56 Å. The structure was determined by obtaining phases directly from the structure-factor magnitudes by means of the symbolic addition procedure. For 1580 non-zero reflections, the final R is 0.147. The crystal structure shows that the packing unit is an “ion-pair” consisting of one di-valent anion and two mono-valent cations. The anion is sandwiched by two cations with weak charge-transfer interaction between them; the closest atomic contact is 2.99 Å. These units stack infinitely, forming a column, along the a axis. Between these stacking columns, there exists a hydrogen bond (N–H···N, 2.84 Å) along the b axis. The (C10N6)2− anion has a C2-2 symmetry; cyano-substituents are tilted out of the plane formed by four central carbon atoms, and the anion takes a propeller shape. The one arm is rotated 13° from the completely planar conformation, while the other two are rotated 24°. On the other hand, the (C9NH8)+ cation seems not to be planar.
Salt and Medium Effects on H− Indicators
Authors: Chattanathan N , Kalidas C 
Published: July 2006

Abstract
The activity coefficients of the molecular forms of a few nitrodiphenylamine indicators were determined by a solubility method in basic solutions of ethylene and propylene glycols. The medium effects on the ions of these indicators were also obtained by determination of the medium effects of their molecular forms separately by solubility measurements. Variation of the activity coefficients and the medium effects on the ions of the indicators are discussed.