bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spectrophotometric Study of the Solution Equilibria between Eriochrom Black T and Zinc(II)-Nitrilotriacetate or Copper(II)-Cyclohexanediaminetetraacetate
Authors: Kodama Mutsuo , Ebine Hide 
Published: July 2006

Abstract
The solution equilibria between Eriochrom Black T (BT) and the zinc(II)-NTA or copper(II)-CyDTA chelate were studied spectrophotometrically, and the stability constants and the compositions of 1-to-1 chelates of BT with these metal ions were determined. Under the experimental conditions employed, irrespective of pH, copper(II) forms only a normal chelate, CuD−, with BT, the stability constant of which is 1021.98(μ=0.10). Zinc (II), however, forms a normal chelate, ZnD−, at pH values lower than 9.00 and a mixed chelate, ZnDX4−, with BT and NTA at pH values higher than 9.00. The stability constant for ZnD− was determined to be 1012.76 (μ=0.10) at pH 8.50, in good agreement with the value reported by Schwarzenbach, and that for ZnDX4−, 1015.38 (μ=0.10).
Studies of the Mixed Amino-acid Complexes of Cobalt(III). II. A Complete Series of [Co(ox)x(gly)y(en)z] Complexes
Authors: Matsuoka Nobuko , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
Five new complexes, C1-cis(O)[Co(gly)2(en)]Br·3H2O, C2-cis(O)-[Co(gly)2(en)]Br·H2O, trans(N)-K[Co(ox)(gly)2], C1-cis(N)- and C2-cis(N)-Na[Co(ox)(gly)2], have been synthesized. The geometrical isomers of both the [Co(gly)2(en)]+ and the [Co(ox)(gly)2]− complex have been separated by ion-exchange column chromatography. The geometrical structures have been determined on the basis of the visible absorption spectra and of the NMR spectra, and from a consideration of the reaction processes of derivation. The visible and near-ultraviolet absorption spectra of a complete series of the sixteen complexes of the [Co(ox)x(gly)y(en)z] type, have been measured and discussed.
The Stereochemistry of Hydrogenation and Hydrogenolysis. VIII. The Stereochemistry of the Reduction of 2-Acetoxy-1-tetralone and 3-Acetoxy-4-chromanone
Authors: Hanaya Kaoru 
Published: July 2006

Abstract
2-Acetoxy-1-tetralone (VI) and 3-acetoxy-4-chromanone (VII) were reduced with a metal hydride complex and by catalytic hydrogenation; the main products of the reduction were found, to be cis-forms. These results indicate that, in the catalytic hydrogenation, the acetoxyl groups at the C-2 position of VI and at the C-3 position of VII hinder these carbonyl compounds from being adsorbed on the catalyst; also, in the reduction with metal hydride complex, the acetoxyl groups exert a steric hindrance upon the approach of the hydride ion to the carbonyl carbon atom.
Kinetic Studies of Bimolecular Nucleophilic Substitution. I. Rates of SN2 Reactions of Phenacyl Bromide with Sodium Phenoxides and Sodium Carboxylates in 50% Aqueous Acetone
Authors: Okamoto Kunio , Kushiro Hajime , Nitta Issei , Shingu Haruo 
Published: July 2006

Abstract
The rates of the bimolecular nucleophilic substitution (SN2 reactions) of phenacyl bromide with sodium para-substituted phenoxides, sodium para-substituted benzoates, and sodium aliphatic carboxylates have been measured in 50% aqueous acetone at 10–70°C. Linear free-energy relationships between the nucleophilic reactivities and basicites (expressed in terms of the pKa’s of the conjugate acids) have been observed in the reactions of para-substituted aromatic nucleophiles, whereas no linear relationships have been seen in the reactions of aliphatic carboxylates except in the cases of sodium acetate, sodium formate, and sodium monochloracetate. An equation, logk2=αpKa+const., has been applied to these reaction series and to the 30 literally-known series of SN2 reactions. The correlation coefficients have then been calculated as a measure of the precision of these linear relationships. Hammett’s ρ values for the reactions of para-substituted aromatic nucleophiles have also been calculated, and the several factors which affect the linear relationships have been discussed.
The Reaction of Nitrosyl Chloride and of Nitryl Chloride with 2-Cholestene
Authors: Terada Akira , Hassner Alfred 
Published: July 2006

Abstract
In connection with our studies on introduction of nitrogen functions into steroids we investigated the addition of nitrosyl chloride and of nitryl chloride to 2-chlestene. Addition of nitrosyl chloride to 2-cholestene followed by dehydrohalogenation with pyridine leads to 2-nitro-2-cholestene as the only isolable product. The formation of nitro addition products is not attributable to the reaction of the olefin with nitryl chloride since the latter reacts with 2-cholestene to give mainly 2β, 3α-dichlorocholestane and 3α-chloro-2β-cholestanyl nitrate.
The Aconite Alkaloids. XXXVII. Anhydro-diacetyldelcosine (Anhydrodiacetyllucaconine) and Its Novel Hydrogenation
Authors: Amiya Takashi , Shima Takeo 
Published: July 2006

Abstract
Delcosine (lucaconine) and its derivatives have all been shown to lose one mole of water, upon treatment with acetyl chloride, thus giving an anhydro compound. On the basis of the observation of the infrared spectra of anhydro-diacetyldelcosine, anhydro-oxodelcosine, and anhydro-1, 10-didehydro-oxodelcosine, it may be concluded that, in each compound, dehydration takes place between two tertiary hydroxyl groups, with a ketone carbonyl group being formed. Based on a tentative structure for delcosine proposed by Marion and his co-workers, structures for anhydro-diacetyldelcosine and anhydro-oxdelcosine are proposed. On hydrogenation over platinum in acetic acid, anhydro-diacetyldelcosine yielded anhydro-dihydro-diacetyl-delcosine. Anhydro-oxodelcosine was inert under these reduction conditions. On the basis of these experimental results, a possible mechanism of this novel hydrogenation is proposed. The ultraviolet spectrum of anhydro-diacetyldelcosine, with a new type of chromophore, is also shown.
Reactions of Aldehyde Caused by Tris(trimethylsiloxy)aluminum
Authors: Saegusa Takeo , Kitagawa Sadao , Ueshima Takashi 
Published: July 2006

Abstract
Reactions of n-butyraldehyde caused by tris(trimethylsiloxy)aluminum were examined and compared with those caused by aluminum t-butoxide. In the Tishchenko reaction of aldehyde caused by aluminum t-butoxide, the t-butoxy group was first transferred from aluminum to the carbonyl group of n-butyraldehyde to produce t-butyl n-butyrate. On the other hand, we observed no formation of trimethylsilyl n-butyrate by the transfer of the trimethylsiloxy group to n-butyraldehyde. However, esters of the n-butyric acid of n-butanol and the glycol derived from the aldol of n-butyraldehyde were found in the system with tris(trimethylsiloxy)aluminum: their formation was ascribed to the aluminum alkoxide species which was first formed between tris(trimethylsiloxy)aluminum and the aldol of n-butyraldehyde. The above assumption has been supported by the finding that aluminum t-butoxide caused the Tishchenko reaction of benzaldehyde, producing benzyl benzoate almost quantitatively, whereas tris(trimethylsiloxy)aluminum did not cause any change because aldol condensation was impossible for benzaldehyde.
Azetidines. I. Addition to Multiple Bonds and Condensation with Carbonyl Groups
Authors: Chen Teng-yueh , Kato Hiroshi , Ohta Masaki 
Published: July 2006

Abstract
The addition of azetidine to α,β-unsaturated esters and to acrylonitrile was studied. Azetidine was condensed with ketones to give the corresponding enamines.
Organic Syntheses by Means of Noble Metal Compounds. XXVIII. Syntheses of a New Type of π-Allylic Palladium Complexes from α, β- and β, γ-Unsaturated Esters and Their Carbonylation
Authors: Tsuji Jiro , Imamura Shinzo 
Published: July 2006

Abstract
A general method of synthesizing a new type of π-allylic complex of palladium from compounds with an allylic hydrogen activated by a carbonyl group is described. Ethyl 3-butenoate and ethyl 2-butenoate give the same carbethoxy-substituted π-allyl complex, with hydrogen chloride eliminated, when treated with palladium chloride. Unsaturated diesters, such as diethyl glutaconate and diethyl 3-hexenedioate, also react with palladium chloride to give the corresponding π-allylic complexes. The structures of these complexes are discussed by means of a study of their NMR spectra. The carbonylation of these complexes proceeds smoothly, and carbon monoxide is introduced to form unsaturated esters. 3-Butenoate and then glutaconate are prepared, starting from allyl chloride, by a series of complex formations and carbonylation reactions. The possible synthetic application of this method of step-by-step introduction of carbon monoxide to other olefins is suggested. Diethyl 3-hexenedioate gives the complex, which is then converted into diethyl muconate by the elimination of palladium by the action of a base or carbon monoxide.
The Surface Area of the Annealed Palladium Foil Catalyst as Determined by a Novel Method of Measuring a Small Surface Area
Authors: Kabe Toshiaki , Mizuno Toshihiko , Yasumori Iwao 
Published: July 2006

Abstract
In order to measure the small surface area of metal foils down to a few ten square centimeters by making use of gas adsorption, an apparatus was developed, which made it possible to estimate the amount of adsorbed xenon at 77.5°K from the desorption of the gas on the surface by moving the foil from the adsorbing bulb into the hot furnace; the change in the surface area of palladium foil catalysts which had been annealed at various temperatures was followed by the use of this method. The roughness factor, the ratio of the real surface area to the geometrical one, of the palladium foil decreased from 1.7 to 1.1 with the progress of annealing at 150–300°C, but it increased to 1.9 after heating at 400°C and then decreased again under treatment at high temperatures to 1.0 for 800°C. The chemisorption of carbon monoxide on the same foil catalyst, which is often used for the surface-area determination, was also studied, and the difference between the adsorbed states of the respective molecule on the palladium surface was briefly discussed in order to compare these methods.
A General Theory of Gel Formation with Multifunctional Interunit Junctions
Authors: Fukui Kenichi , Yamabe Tokio 
Published: July 2006

Abstract
A theory is presented for a general treatment of the molecular size distribution, the gel point, and the post-gelation phenomena with respect to polymerization with formations of various kinds of interunit junctions, assuming (1) that all functional groups are equally reactive, and (2) that no kind of intramolecular interunit junction occurs. These interunit junctions appear concurrently in a system composed of a mixture of monomeric molecules and with a distributions of functionalities. Two cases are treated: (1) when the interunit junction is characterized only by the number of functional groups involved in its formation, and (2) when the interunit junction is characterized not only by the number of groups, but also by the magnitude of the free energy of its formation. The former is illustrated by the poly condensation with bi- or terfunctional interunit junctions or with both. The latter is illustrated by the polycondensation between A and B groups in a mixture of A-monomers with equireactive A groups and B-monomers with equireactive B groups, where a B-monomer is regarded as a kind of interunit junction.
Infrared Spectra of Urea and Thiourea Thin Films on the Metal Surface
Authors: Suëtaka Wataru 
Published: July 2006

Abstract
The infrared spectra of thin urea and thiourea films, several hundred Angstroms thick, on a steel plate were obtained using an optical system in which the beam polarized parallel to the plane of incidence was incident at 70° upon a steel plate covered with film. The spectra obtained showed that the c-axis of the urea crystal was parallel to the metal surface. However, the abnormal behavior of the NH2 bending and the NH2 twisting bands suggests that the urea molecule in the film was deformed from the planar structure. The intensities of the infrared bands of thiourea belonging to the B1 species decreased in the film, and it may be concluded that the c-axis of the crystal is nearly parallel to the metal surface. The considerable rise in frequency of the NH2 wagging band observed in the thin thiourea film may arise from the deformation of the crystal. As for the thioureacollodion film, thiourea A1 bands appeared to be very weak, corresponding to the C=S bond orientation parallel to the metal surface. The dichroism of the thiourea bands in the 3 μ region obtained about the thiourea and thioureacollodion thin films is in agreement with the Badger-Waldron assignment of the absorption bands.
The Liquid Phase Oxidation of Acrolein. IV. A Postulated Configuration of the Divalent Cobalt Acetylacetonate Catalysts in the Initiation Reaction
Authors: Ohkatsu Yasukazu , Osa Tetsuo , Misono Akira 
Published: July 2006

Abstract
A possible configuration of the pale blue precipitated divalent cobalt catalyst, synthesized by the addition of a saturated solution of deionized water in acrolein to a vigorously stirred solution of Co(acac)2 in benzene, is deduced from the infrared spectrum and thermal analyses; it is considered to be Co(acac)2-H2O-acrolein, in which acrolein is coordinated through its aldehyde oxygen. When the precipitated catalyst is used in the oxidation of acrolein, the induction period of oxygen absorption is shorter, the rate of oxygen absorption is higher, and the amount of oxygen absorbed is more than when any other divalent cobalt-acetyl-acetonate are employed. From these results, it is considered that the precipitated catalyst contains a species which is converted into a more active trivalent form faster than the other divalent catalysts. Furthermore, Co(acac)2 and Co(acac)2·2H2O are considered to take part in the oxidation via Co(acac)2-H2O-acrolein.
Acetonation of l-Sorbose by Ketal Interchange
Authors: Maeda Takashi 
Published: July 2006

Abstract
The acetonation reaction of l-sorbose with acetone dimethyl ketal was investigated. The products and the yields were greatly influenced by the reaction conditions. The reaction at 45°C gave 1, 3 : 4, 6-di-O-isopropylidene-β- (VIIa), 1, 2 : 4, 6-di-O-isopropylidene-α- (Va) and 2, 3 : 4, 6-di-O-isopropylidene-α-l-sorbofuranose (IVa) and the β-anomer of Va (VIa). At the refluxing temperature, the reaction afforded IVa and the 2-O-methyl derivative of VIIa (VIIe), while at room temperature it yielded 1, 2 : 3, 4-di-O-isopropylidene-α-l-sorbopyranose (VIIIa), 1, 2 : 4, 5-di-O-isopropylidene-α-l-sorbopyranose (IXa), and 5-O-α-methoxyisopropyl-1, 2 : 3, 4-di-O-isopropylidene-α-l-sorbopyranose (VIIIc).
Use of Anhydrous Hydrogen Fluoride in Peptide Synthesis. I. Behavior of Various Protective Groups in Anhydrous Hydrogen Fluoride
Authors: Sakakibara Shumpei , Shimonishi Yasutsugu , Kishida Yasuo , Okada Masanori , Sugihara Hideo 
Published: July 2006

Abstract
The properties of anhydrous hydrogen fluoride (HF) as a reagent for the acidolysis of various protective groups have been studied. Amino acids with various protective groups were each treated with HF at 0 or 20°C in the presence of anisole, and the reaction products were tested. Thus, HF was found to be much better than the other known reagents, such as hydrogen bromide and trifluoroacetic acid. In the present study, the following groups were shown, for the first time, to be removed safely: the nitro group in nitroarginine, the diphenylmethyl group in diphenylmethylamide, the t-butyl group in S-t-butylcysteine, the isopropyloxycarbonyl group, and the isopropyl ester group. A new and convenient apparatus was designed for the safe handling of HF for peptide synthesis.
Asymmetric Synthesis with Sugar Derivatives. III. Action of Methylmagnesium Iodide on Sugar Esters of Phenylglyoxylic Acid
Authors: Kawana Masajiro , Emoto Sakae 
Published: July 2006

Abstract
Asymmetric synthesis of atrolactic acid was investigated by the reaction of methylmagnesium Iodide with phenylglyoxylic ester containing such an optically active component as 1,2 ; 5,6-di-O-cyclohexylidene-d-glucose, its isopropylidene derivative 5-O-ethyl-1,2-O-isopropylidene-d-xylose, its 5-deoxy-5-S-ethyl derivative, or 5-deoxy-1,2-O-isopropylidene-d-xylose. All of the resulting sugar atrolactates were very easily hydrolyzed with alkali at room temperature to afford the levorotatory acid in 22–38% optical yield. The asymmetric reactions proceeded in accordance with Prelog’s rule, but a Prelog’s scheme for asymmetric induction was slightly modified when the steric course for 3-O-phenylglyoxyloyl-1,2 ; 5,6-di-O-cyclohexylidene- and -isopropylidene-d-glucose was discussed.
On the Elastomers Derived from Polybutadiene-Acrylic Acid-Acrylonitrile Terpolymer as a Fuel Binder
Authors: Tokui Harusuke , Yamazaki Kiroku 
Published: July 2006

Abstract
Some characteristic properties of a polybutadiene - acrylic acid - acrylonitrile terpolymer (PBAN) and of the elastomers derived from it were determined to obtain the fundamental information as fuel binders for propellants. The chemical composition of the prepolymer (RF-2) was determined to be:
[{−CH2−CH=CH−CH2−}84.0{−CH2−CH(CN)−}12.6{−CH2−CH(COOH)−}3.4]n,
and it was found to be a Newtonean fluid. Since the prepolymer was found to be, on the average, 1.2 functional, much mono- or non-functional portion is probably included in it. The tensile properties of the elastomer, based on the cured PBAN, were not as good as those of telechelic elastomers, as far as the same curing agents were concerned. This may be attributed to the influence of the random distribution of the cross-linking sites and to that of the resultant terminal sections of the elastomer. The ultimate tensile strength and ultimate elongation of the PBAN elastomers were in the range of 3–6 kg/cm2 and 100–400% respectively. It should be remembered that the elastomers contained as much as 30–50% sol fractions.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. II. The Anion Radicals of Diesters of o-, m- and p-Phthalic Acids
Authors: Hirayama Masatoshi 
Published: July 2006

Abstract
The ESR spectra have been observed for the anion radicals of several diesters of o-, m- and p-phthalic acids. The radicals were generated by the electrolytic reduction in acetonitrile and also by the reduction with lithium, sodium, potassium and cesium metals in dimethoxyethane (DME) and tetrahydrofuran (THF). The MO calculations of spin densities were made for these radicals by using McLachlan’s method, and the calculated spin densities for the anion radicals of m- and p-phthalates were in good agreement with the experimental splitting constants obtained by electrolysis. In the anion radicals of o-phthalates, the results of calculations taking into account the steric effect between the two ester groups revealed that the twisting angle between each ester group and the ring was 35–45°. From the spectrum of di-t-butyl p-phthalate anion radical prepared by the electrolysis in DME, the t-butyl ester group was found to be in a fixed orientation, probably planar with the ring. It was suggested that an ion complex was formed between the o- or p-phthalate anion radical and each alkali metal cation, and that in the p-phthalatesodium system in DME or THF there existed an equilibrium between an ion complex and a completely dissociated state.
The Crystal Structure of the Phenazine-Iodine Molecular Complex
Authors: Uchida Tokiko 
Published: July 2006

Abstract
The 1 : 1 molecular complex of phenazine and iodine crystallizes in an orthorhombic system with the space group Pbcn. There are four formula units in a unit cell with the dimensions of a=12.85, b=11.69, and c=8.30 Å. The structure was solved by Patterson methods and was refined by two-dimensional Fourier and (F0–Fc) syntheses. The component molecules are arranged alternately along the b axis, the two nitrogen atoms of the phenazine molecule and the two iodine atoms of the iodine molecule lying on a two-fold axis. The molecules of each component are stacked in individual columns parallel to the c axis, where the mean separations of the molecules satisfy the van der Waals distances. The phenazine molecule is planar within the range of experimental error. The interatomic distance of an iodine molecule is 2.75 Å; this is more from that of a free molecule, but not as large as those of the other iodine complexes. The charge-transfer interaction between phenazine and iodine is a little weakened by the steric hindrance of hydrogen atoms attached to the phenazine nucleus.
Photochemical Reaction between Acridine and Acridan in the Presence and in the Absence of Oxygen. I. Studies by the Steady Light Illumination
Authors: Niizuma Shigeya , Ikeda Yoshinori , Koizumi Masao 
Published: July 2006

Abstract
Photochemical reactions between acridine and acridan in benzene solution have been studied. The product is diacridan in the absence of oxygen, while in the presence of oxygen, it is acridine. The reactive excited state in both cases is, most likely, the lowest π-π* triplet state. Contrary to the expectation, the kinetics in the degassed solution is difficult to interpret. The rate of acridine production in the presence of oxygen, gives a sharp maximum near ∼10−4 m of oxygen at fixed acridan concentrations. Its quantum yield is reproduced by Φ=0.25×β[AH2]/(α[O2]+β[AH2]) with α/β=3.3 (1). Two schemes consistent with (1) have been tentatively presented in which one involves the mere deactivation of the triplet acridine by oxygen, and the other assumes the formation of an excited oxygen (or the like), which oxidizes acridan but is partially deactivated by a certain substance.
Fluorescence Quenching and the Charge Transfer in the Excited State. II. Dimethylnaphthylamine-Dimethyl Phthalate in Various Solvents
Authors: Kaneta Kyoichi , Koizumi Masao 
Published: July 2006

Abstract
As an extension of a previous paper (Bull. Chem. Soc. Japan, 39, 2588 (1966)), the quenching action of p-methyl toluate, ethyl benzoate, dimethyl esters of m-, o-, p-phthalic acids on the fluorescence of N, N-dimethyl-2-naphthylamine has been studied in several solvents. The quenching constants of the above substances (in the above sequence) in cyclohexane and dimethylformamide are respectively (0.5, ∼1, 65, 85, 93) and (41, 58, 103, 85, 124). The order, toluate&lt;benzoate&lt;phthalate, is consistent with the charge transfer mechanism of quenching in which fluorescer and quencher act respectively as a donor and an acceptor. In slightly or nonpolar solvents a new emission attributed to an excited CT complex has been found; its intensity has been the strongest in the case of dimethyl m-phthalate. Using this substance as a quencher, solvent effect on the quenching efficiency and the CT emissivity has been studied. It has been found that in weakly polar solvents, these two quantities decrease similarly with the increasing solvent polarity, whereas in highly polar solvents the former is large and the latter is negligible. The results in less polar solvents suggest that the reorientation of the solvated molecules is an essential process for both the quenching and the CT emission. Another evidence for this view has been found in the experiments with mixed solvents. In highly polar solvents, the production of free radical ions is most plausible but the possibility of the formation of a solvated ion pair with no emissivity, cannot be ruled out.
Theoretical Studies of the Second Virial Coefficient of the Copolymer Near the θ Temperature
Authors: Sato Hiroshi , Kamada Kensuke 
Published: July 2006

Abstract
The osmotic second virial coefficients of random and block copolymers are calculated according to the perturbation theory. Evaluation is carried out to the double-contact approximation. The results show that the expressions for the osmotic second virial coefficients of random and block copolymers have different forms in their second term. The so-called “theta” temperature of the block copolymer at which the second virial coefficient vanishes, is found to be higher than that of the random copolymer. These results are compared with some existing experimental results. It is also suggested that the “theta” temperature of a copolymer having a distribution of the sequence length of two monomers is located between those of the random and two-block copolymers.