bluuebunny/crossref_metadata_2025 huggingface dataset:
Stability Order in Metal Chelate Compounds. IV. 2-Pyridylmethanol Complexes
Authors: Murakami Yukito , Takagi Makoto
Published: July 2006

The complexing behavior of 2 - pyridylmethanol with magnesium(II), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been studied in aqueous media at 25.0±0.1°C and an ionic strength of 0.10 m (KNO3). The stability constants for the 1 : 1 (ligand to metal) complexes of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) with the neutral 2-pyridylmethanol and also for the 2 : 1 complexes of nickel(II) and copper(II) have been evaluated. The resulting stability order with respect to the bivalent metals has been found to follow the sequence:

Cd(II)<Mn(II)<Zn(II)<Co(II)<Ni(II)<Cu(II)

The higher stability of the present complexes relative to the corresponding pyridine complexes may be ascribed to the formation of a chelate ring which involves the hydroxyl group of the ligand.

After the complex formation between metal ions and the neutral ligand has proceeded to a certain extent, the liberation of a hydroxyl proton from the complex was observed to occur in several metal complex systems. This tendency was greatest for the copper complex, followed by the zinc, nickel and cobalt complexes in this order. Acid dissociation constants for the 1:1 and 2:1 copper complexes have also been evaluated.

Several pieces of evidence have been obtained in support of the coördination ability of the hydroxyl group of the present ligand in its anionic form.

The neutral copper chelate, bis(2-pyridylmethanolato)copper(II), as well as other various copper 2-hyridylmethanolate chelates which involve acetate, chloride, iodide, nitrite and thiocyanate ions as the third component, has been isolated. Acetato(2-pyridylmethanolato)-copper(II) has been found to exist as the tetrameric form in chloroform.
Small Ring Compounds. VII. The Syntheses of 3-Oxabicyclo-[3.1.0]hexane and Its Derivatives
Authors: Shono Tatsuya , Oku Akira , Morikawa Takeshi , Kimura Masatoshi , Oda Ryohei
Published: July 2006

Some bicyclic ethers containing a cyclopropane ring, i.e., 3-oxabicyclo [3.1.0] hexane derivatives, have been synthesized. Two methods have been used in the syntheses of these compounds. One of them has been the dehydration of cis-1,2-dimethylolcyclopropane derivatives, and the other, the addition of some carbenes to 2,5-dihydrofuran. The Simmons-Smith method has also been adopted. The NMR spectra of these bicyclic ethers have been examined. The types of their spectra are fairly simple. The chemical shifts and the coupling constant of some protons have also been measured. Attempts to polymerize these bicyclic ethers, unfortunately, have been unsuccessful.
The Electronic Spectra of Aniline and N-Methylaniline Adsorbed on Aluminum Chloride. I
Authors: Sato Hiroyasu , Hirota Kozo , Nagakura Saburo
Published: July 2006

The electronic spectra of aniline and N-methylaniline adsorbed on evaporated film of aluminum chloride have been measured (150–300 mμ for the former adsorbate and 185–300 mμ for the latter). In the case of N-methyl-aniline, a spectrum which is nearly the same as that of ethylbenzene has been obtained. In the case of adsorbed aniline, the spectrum shows features intermediate between those of the aniline vapor spectrum and those of the toluene vapor spectrum. These results can be interpreted in terms of the electron donation from the lone-pair electrons on the nitrogen atom of these molecules to some electron-accepting center on aluminum chloride, presumably to the vacant sp3-orbital of the aluminum atom on the surface, resulting in the weakening of the conjugation between the amino- (or N-methylamino-) group and the benzene ring. The positions of the absorption bands are interpreted qualitatively in terms of the relative location of charge-transfer and locally-excited configurations in these molecules.
Formation Constants of Sulfato, Acetato and Sulfatoacetato Complexes of Copper(II) at Ionic Strength 1.0
Authors: Tanaka Nobuyuki , Saito Yu , Ogino Hiroshi
Published: July 2006

The polarographic method for the determination of the formation constants which is based on the measurement of the effects of acetate and/or other co-existing ions on the equilibrium of the substitution reaction, M+M′L\ightleftarrowsML+M′, has been developed, and applied to the study of the copper(II) complexes with acetate and/or sulfate ions. The formation constants obtained at 25°C and ionic strength 1.0 are: 2·0×10 for KCu(OAc), 1·1×102 for KCu(OAc)2, < 3 for KCuSO4, ∼3×10 for KCu(SO4)2, 4×10 for KCu(OAc)(so4) and ∼7×10 for KCu(OAc)(SO4)2.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. VIII. A New Method for the Determination of Cadmium
Authors: Kotsuji Keiya
Published: July 2006

A new method for the determination of cadmium has been proposed. The method is based upon solvent extraction of the associated complex formed between 2,2′-dipyridyl iron(II) chelate cation and tetraiodo-cadmium complex anion and upon estimation of the absorbance due to the chelate cation in the organic phase.
The NMR Signal Shape of Identical Nuclei Exchanging between Two Different Environments
Authors: Nakagawa Toshio
Published: July 2006

The Gutowsky-Holm equation has been transformed into a formula which expresses the signal as a function of dimensionless parameters (a=2πτ|νA–νB|, r=1⁄2πT2|νA–νB| and pB) and a dimensionless variable (f=(ν–νA)/(νA–νB)). The shape function in this form is convenient for graphic representation and can be easily calculated for a desired combination of the parameters by using a suitable computer. The exchange rate can be determined by searching for a theoretical curve that agrees with the shape of the experimental signal.
The Surface Adsorption of Sodium Alkyl Sulfates from Dioxane-Water Mixtures
Authors: Shirahama Keishiro , Nakao Kiyoshi , Endo Hiroko , Matuura Ryohei
Published: July 2006

The surface adsorptions of three sodium alkyl sulfates (C12, C14, C16) from dioxane-water mixtures have been measured by using 35S-labeled surfactants; it has been found to decrease with an increase in the dioxane concentration. This decrease has been explained in terms of the following factors; (1) the variation in the standard chemical potential of the surfactant in the bulk phase, or the free energy of transfer, (2) the surface tension of the solution, and (3) the dielectric constant of the solvent. In a solvent containing more dioxane than 40wt.%, it has been shown, both by experiment and by theory, that these alkyl sulfates lose their surface activities.
The Coprecipitation Behavior of Rare Earth Elements with Calcium Oxalate upon Precipitation from a Homogeneous System
Authors: Matsui Masakazu
Published: July 2006

The effects of the pH value, the concentration of organic acid and several other variables upon the distribution coefficient were studied for the coprecipitation process of the calcium-lanthanide oxalate system. The logarithmic distribution law was followed in all cases of the coprecipitation of rare earth elements. Of the several variables studied which affected the logarithmic distribution coefficient, the most important were the pH value and the concentration of an organic acid. The coefficient decreased as the acid anion content increased. This can be attributed to the fact that the acid anion formed complex compounds with lanthanide and calcium. The distribution coefficients of several rare earth elements in producing the precipitate from a similar solution were closely related to their basicity or to the solubility of their oxalate salts. The order of the magnitude of the distribution coefficient was as follows: Lu>Y>Eu>Ce; this was in the reverse order of the basicity of rare earth elements or of the solubility of their oxalate salts.
Studies of Aminosugars. XI. Configurational Studies of Aminosugar Glycosides and Aminocyclitols by a Copper Complex Method
Authors: Umezawa Sumio , Tsuchiya Tsutomu , Tatsuta Kuniaki
Published: July 2006

An extensive study has been made of the determination of the rotational shift of aminosugars in three kinds of cuprammonium solutions, i. e., in solutions of tetramminecopper(II) sulfate, ammoniacal cuprous chloride and Cupra B, with special consideration of the spacial relationships between adjacent amino and hydroxyl groups in six-membered chair molecules. This paper is an extension of the work of Reeves which provided a tool for the determination of the spacial relationships between adjacent two-hydroxyl groups. Some significant generalizations have been obtained. About ten derivatives of glucosamine have been prepared, and their structures, as indicated by their rotational shifts, have been discussed. The absolute configurations of d- and l-trance-2-aminocyclohexanol have been successfully determined.
Organic Sulfur Compounds. VI. The Reactions of Arylsulfinic Acids with Alkyl Chlorocarbonates
Authors: Kobayashi Michio , Terao Miki
Published: July 2006

The reactions of the arylsulfinic acid salts with alkyl chlorocarbonates in various alcohols as solvents gave the alkyl sulfinates, in which the alkoxyl groups originated from the solvent alcohols, not from the chlorocarbonates. Sodium p-toluenesulfinate-18O and ethyl chlorocarbonate in a large excess of methanol gave methyl p-toluenesulfmate-18O, which was shown to contain about half of the 18O atoms of the starting salt. The mixed anhydride of sulfinic acid and monoalkyl carbonate is postulated as an intermediate, the alcoholysis of which would give the sulfinate ester. Reactions have been studied also in the nonhydroxylic solvents.
The Non-Newtonian Flow of Poly(Dimethyl Siloxane)
Authors: Ito Yoshio
Published: July 2006

The non-Newtonian flow of poly (dimethyl siloxanes) with a wide variety of degrees of polymerization (Z), 31.6 to 6.02×103, was studied by using short capillary viscosimeters. Measurements were performed in the range of rate of shear from 10−1 to 3×106 sec−1. It was found that the flow behavior was markedly affected by the value Z of the test materials. That is, the flow was practically Newtonian over the entire range of shear rates when Z was less than 1.55×102. For higher values of Z, however, typical non-Newtonian behavior was observed in the range of moderate shear rates. At extremely high shear rates, the materials with Z=3.23×102 to 2.63×103 exhibit the upper (or second) Newtonian flow, but the materials with still higher values of Z exhibit the spiral flow. It was also found that the Shishido equation (J. Chem. Soc. Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 84, 889 (1963)) was applicable to this polymer in describing the observed viscosity vs. shear rate dependence. Finally, an empirical method was proposed for estimating the upper Newtonian viscosity value from the viscosities at zero shear stress and at the inflection point of the flow curve.
A Spectroscopic Study of Alkylnitrobenzene Anion Radicals
Authors: Nakai Yasuto
Published: July 2006

A series of alkylnitrobenzene anion radicals has been studied by both electron spin resonance and infrared spectroscopy. It has been shown that there is a relationship between the magnitude of the nitrogen hyperfine splitting constant and the steric effect of the bulky alkyl group adjacent to the nitro group. In addition to the physical deformation factors, the effects of solvents, counter-ions, and temperature variation have been discussed. In the infrared spectra, the differences between anion radicals and neutral molecules have been found to be small, except for the change in the absorption intensity of the nitro-group stretching vibration.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. XI. The Nitrates of Some Hexoses
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko , Yamada Noriko
Published: July 2006

The rotatory dispersions (RD) and the ultraviolet absorptions of eight nitrates of galactopyranoside, altropyranosides, glucofuranoside, mannopyranosides and of glucopyranosides, and also of five hexosepyranosides, have been measured. Studies have also been made of the correlation between the configuration and the Cotton effect, the sign of which has been determined by the RD curve as well as by the dispersion constant computed from the dispersion data, and in some cases by means of the circular dichroism (CD). All the findings and conclusions are consistent with the generalized rule originally found with glucose derivatives (Y. Tsuzuki, K. Tanabe and K. Okamoto, This Bulletin, 39, 761 (1966)). The rule has been shown to be extensively applicable to several hexoses; namely, α-glycosides with a C–ONO2 chromophore of a β(or d)-configuration show negative Cotton effects, and those with a C–ONO2 group of a β(or l)-configuration exhibit positive Cotton effects, while with nitrates of β-glycosides the signs of the Cotton effects are exactly reversed (ref. Conclusion).
Organic Syntheses by Means of Noble Metal Compounds. XV. The Carbonylation of 1, 5, 9-Cyclododecatriene Catalyzed by Palladium
Authors: Tsuji Jiro , Nogi Tatsuo
Published: July 2006

The carbonylation of 1, 5, 9-cyclododecatriene has been carried out in ethanol in the presence of palladium chloride; mono- and diesters have thus been obtained without ring contraction. It has been observed, by means of a study of the NMR and infrared spectra, that the first attack of carbon monoxide occurred at the trans double bond, giving ethyl cyclododecadienecarboxylate. The second attack of carbon monoxide occurred randomly, giving an isomeric mixture of ethyl cyclododecenedicarboxylate. No triester was obtained even under prolonged carbonylation. The true catalyst has been found to be metallic palladium, and the presence of hydrogen chloride has been found to be essential for the catalysis. The oxidation of ethyl cyclododecadienecarboxylate, followed by esterification, has given ethyl succinate and 1, 3, 6-hexanetricarboxylate. This result indicates that the double bonds of ethyl cyclododecadienecarboxylate remain at the original positions.
The Crystal Structure of Succinonitrilo-disilver Nitrate, 2AgNO3·NC(CH2)2CN
Authors: Nomura Teruo , Saito Yoshihiko
Published: July 2006

The structure of 2AgNO3·NC(CH2)2CN has been determined by X-ray analysis. It is mono-clinic; a=5.87, b=17.79, c=4.61 Å, β=118.2°, space group P21⁄a, two formula units in the cell. The structure is essentially ionic and consists of the complex cations, [AgNC(CH2)2CNAg]2+ (Ag–N, 1.97 Å), and the nitrate anions. All the bond lengths are normal. The molecule of succinonitrile was found to take the trans configuration; this is in conformity with the conclusion drawn from the infrared study.
A Mass Spectrometric Study of Phosphorus Oxide
Authors: Hashizume Akio , Wasada Nobuhide , Tsuchiya Toshikazu
Published: July 2006

Phosphorus pentoxide has been investigated with a mass spectrometer over the temperature range from 60°C to 650°C. A Knudsen cell has been installed in the source of the mass spectrometer. Two samples were used in the experiment. One was commercially-available phosphorus pentoxide, while the other had been purified from the commercial phosphorus pentoxide by Finch’s method. The ionization efficiency curves near the appearance potential of P4O9+ and P4O10+, the fractional yield of each ion versus the ionizing voltage have been investigated and interpreted as evidence for the presence of the P4O9 molecule. Three curves representing the intensity of the mass 284 (P4O10+) peak as a function of the temperature have been obtained. Two of them, which set on at about 250°C and 450°C respectively, are related to the known vapor pressure curves of phosphorus pentoxide. The curve with the lowest onset temperature, about 100°C, may be interpreted as a vapor pressure of a new low temperature phase of phosphorus pentoxide.
Ferrocene-containing Polymers. VIII. Polycondensation of N, N-Dimethylaminomethylferrocene with Ferrocene
Authors: Neuse Eberhard W , Koda Kazuko
Published: July 2006

Based on previous investigations involving the self-condensation of the ferrocenyl Mannich base, N, N-diniethylaminomethylferrocene (I), the present paper describes the co-condensation of this Mannich base with ferrocene. The reactions are conducted in the melt phase in the presence of a ZnCl2/HCl catalyst system. The resulting polymeric products are soluble and partially fusible and have number-average molecular weights in the 500–4000 range (unfrac-donated). The polymers, exhibiting the idealized structure III, are closely related to the products of self-condensation (II), with recurring units composed of ferrocenylene and methylene groups and homoannular substitution predominating along the chain. Due to the presence of ferrocene, however, an additional termination step is introduced into the overall reaction,, leading to a reduced degree of polymerization. The considerable excess over the stoichiometric amount of ferrocene required to achieve this competitive termination and concomitant decrease in Mn suggests that pronounced inductive and hyperconjugative effects are operative in the fer-rocenylene-methylene system, resulting in activation of the methylene-substituted ring. The isolation of the lowest homolog possible, diferrocenylmethane, lends further support to the proposed structure of the recurring unit. Spectroscopic evidence obtained on subfractionated material suggests the substitution pattern along the chain to be essentially the same as in the earlier described homocondensation polymers, which is consistent with the assumption of essentially like propagation mechanisms in both cases. A small degree of branching is also inferred from spectroscopic data.
The Co-occurrence of Isoflavonoids at Different Oxidation Levels
Authors: Suginome Hiroshi , Kio Toshiro
Published: July 2006

Some biogenetic aspects of the co-occurrence of pseudobaptigenin, maackiain and sophorol are discussed.
The Absolute and Relative Stereochemical Correlation of Isoflavanone, Sophorol and Naturally-occurring Isoflavan Derivatives
Authors: Suginome Hiroshi
Published: July 2006

By rotatory-dispersion studies, it was confirmed that sophorol, (−) maackiain, pterocarpin, equol and homopterocarpin have the same absolute configuration at position 3. The results of the O. R. D. examination of (−) halostachine and pterocarpinoids allow us to assign the 3R, 4R configuration to pterocarpin and to the related compounds.
The Viscosity and Conductivity of Aqueous Solutions of Electrolytes Mixed with Glycine and Urea
Authors: Tonomura Tokuzo , Okamoto Katsunobu
Published: July 2006

The viscosities, the densities, and the conductivities of aqueous solutions of electrolytes mixed with glycine or with urea have been measured at 15, 25 and 35°C. The relative viscosities and the relative conductivities of the mixed solutions have been expressed by the empirical formulae, η=η′+η0βC and Λ=Λ0(1−γC), respectively. The retarding effect of glycine on the conductivity of the strong electrolytes has been found to be greater than that of urea in the mixed solutions. The states of the hydration of glycine, urea and the strong electrolytes have been discussed on the basis of the relations between B-values in the viscosity formula of Jones and Dole and the effective volumes in aqueous solutions.
Monolayer Adsorption with Nearest Neighbor Interactions
Authors: Tykodi Ralph J
Published: July 2006

A sequence of approximate combinatorial treatments of the localized monolayer adsorption of a gas on a lattice of uniform sites with only nearest neighbor interactions allowed generates a one parameter family of isotherm equations. For each of those cases where the general lattice problem has been solved exactly, it is possible to find a value of the adjustable parameter such that critical behavior on the lattice in question is reproduced exactly.
Sensitization in the Photoconductance of Polyacenaphthylene
Authors: Hayashi Yoshiki , Kuroda Makoto , Inami Akira
Published: July 2006

The sensitization of the photoconductivity in polyacenaphthylene by a dye and/or a Lewis acid was investigated. The most effective materials are methylene blue (E1⁄2=1500 lux. sec.), rhoda-mine 6G (6000 lux. sec.), and victoria pure blue (6500 lux. sec.) in the dye sensitization, and 1-nitroanthraquinone (1200 lux. sec.), 2, 3-dichloronaphthoquinone (1400 lux. sec.), 1, 5-dichlo-roanthraquinone (1500 lux. sec.), chloranil (1800 lux. sec.), and 2-chloroanthraquinone (1900 lux. sec.) in the Lewis-acid sensitization. The combined effects of a dye and a strong acid were determined in the case of polyacenaphthylene as well as poly-N-vinylcarbazole.
Ammoniak-Synthese an einigen legierten Katalysatoren
Authors: Brill Rudolf , Ohsumi Yoshio
Published: July 2006

Es wird versucht, Eisenkatalysatoren fur die Ammoniak-Synthese herzustellen, bei denen dem Eisen Fremdmetalle (Chrom, Nickel, Kupfer) zulegiert sind. Um Katalysatoren mit einer Struktur zu erhalten, die der Struktur der aus reinem Eisen hergestellten vergleichbar ist, wurden die Fremdmetalle als solche oder als Oxide dem Carbonyleisen beigemischt, das dann in üblicher Weise durch Schmelzen im Sauerstoffstrom in Magnetit übergeführt wurde. Eine Mischkristall-bildung in der Magnetitphase wurde nur bei Nickel und Chrom gefunden. Durch Reduktion der Spinelle wurde nur bei Nickel eine Legierungsbildung festgestellt. Cr2FeO4 war unter unseren Bedingungen (Reduktion bei 400°C mit Wassersoff-Stickstoff-Gemisch) nicht reduzierbar. Alle mit Kupfer hergestellten Katalysatoren zeigten im reduzierten Zustand Kupfer neben Eisen. Die Legierungskatalysatoren mit Nickel zeigten bei Gehalten bis zu 5% Nickel innerhalb der Fehler-grenze dieselbe Aktivierungsenergie wie reines Eisen, wahrend Katalysatoren mit 10—30% Nickel eine merklich geringere Aktivierungsenergie aufweisen, jedoch tritt dabei ein Kompensationseffekt auf.
The Dipole Moments of the Oligomer of Ethylenediamine
Authors: Kimura Ko , Toshiyasu Yoshio , Fujishiro Ryoichi
Published: July 2006

The dipole moments of ethylenediamine (N=1), diethylenetriamine (N=2), triethylenetetramine (N=3), and tetraethylenepentamine (N=4) were measured in a benzene solution at 25°C and 45°C. The observed dipole moments of N=1, N=2, N=3, and N=4 are 1.89 D, 2.22 D, 2.37 D, and 2.56 D respectively at 25°C, and 1.84 D, 2.22 D, 2.36 D, and 2.58 D respectively at 45°C. The dipole moments were theoretically calculated on the assumptions that; (i) the dipole moments of these chain molecules are given by the vector sum of the dipole moments of the polar groups of amine, and (ii) all internal rotations about single bonds are free. The calculated values of N=1, N=2, N=3, and N=4 are 1.84 D, 2.15 D, 2.43 D, and 2.68 D respectively. The agreement between the observed values and the calculated values is satisfactory. It may, therefore, be expected that the molecular chains will be in the random coil state. The intramolecular hydrogenbonding is very weak, as there is no temperature dependence of the observed dipole moments.
A Molecular Compound between Glutamic Acid and Pyroglutamic Acid
Authors: Suzuki Yoshihisa , Nagashima Nobuya
Published: July 2006

A new molecular compound, which consists of l-glutamic acid, l-pyroglutamic acid and water of crystallization in a 1 : 1 : 1 mole ratio, has been discovered. In its crystal, the unit-cell is monoclinic with a=5.10, b=7.20, c=18.38 Å, and β=96.6°C, and the space group has been determined to be P21. Equilibrium measurements in the system of l-glutamic acid, l-pyroglutamic acid and water at 20°C, 30°C, and 50°C, showed that the transition temperature from the molecular compound to l-pyroglutamic acid and α-form l-glutamic acid is 35.5°C, while that to l-pyroglutamic acid and β-form l-glutamic acid is 20.5°C. Thus, the molecular compound is stable only below this temperature. This molecular compound has an incongruent solubility. When it is placed in water, a crystallization of l-glutamic acid takes place as the molecular compound is dissolved. A similar molecular compound consisting of d-glutamic acid and d-pyroglutamic acid is also obtained, but no molecular compound of the l-glutamic acid and d-pyroglutamic acid, or vice versa, is obtainable. On the basis of these facts, an optical resolution is actually possible for glutamic acid. When this molecular compound is heated, it is converted into another molecular compound at about 70°C due to the loss of the water of crystallization; then it is decomposed to l-glutamic acid (β-form) and l-pyroglutamic acid at about 90°C.
Studies of Peptide Antibiotics. IV. The Synthesis of Tyrocidine A
Authors: Ohno Motonori , Kato Tetsuo , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

The synthesis of a cyclic decapeptide, cyclo-l-phenylalanyl-d-phenylalanyl-l-asparaginyl-l-glutaminyl-l-tyrosyl-l-valyl-l-ornithyl-l-leucyl-d-phenylalanyl-l-prolyl, which has an amino acid sequence determined by Craig et al. for natural antibiotics, tyrocidine A, has been described. The chemical and biological properties of the synthetic product have been shown to be in agreement with those of the natural tyrocidine A.
The Knoevenagel Reaction between Hydroxybenzaldehydes and Ethyl Cyanoacetate
Authors: Yasuda Heinosuke , Midorikawa Hiroshi
Published: July 2006

Substituted 2-hydroxybenzaldehydes react with two equivalents of ethyl cyanoacetate to give α-β-(substituted 3-coumarinyl)-β-cyano-β-ethoxycarbonylethylenes in the presence of piperidine. When equivalent aldehyde and the cyanoacetate are used, substituted 2-imino-3-ethoxycarbonyl-2H-chromenes result, without the isolation of arylidenecyanoacetates. In o-hydroxyaryls, salicylic and o-thymotinic aldehydes, which give benzopyrane derivatives, are exceptional cases. 5-Phenylazo- and 5-nitro-2-hydroxybenzaldehydes result in the formation of coumarin derivatives. An abnormal condensation is also shown in the cases of 3, 5-dibromo-2, 4-dihydroxy-, 2-hydroxy-3-methoxy- and 2-hydroxy-4-methoxybenzaldehydes; i. e., the first one yields a 1:1-condensation product, while the last two give 3-cyanocoumarin derivatives, even with an excess of ethyl cyanoacetate. The condensation of m- and p-hydroxybenzaldehydes with ethyl cyanoacetate give the normally-expected arylidenecyanoacetates, even in the presence of a large excess of the cyanoacetate.
Organic Sulfur Compounds. IX. The Reactions of N-Sulfinylamines with Nitrogen Tetroxide and Nitrosyl Chloride
Authors: Kobayashi Michio , Honda Koichi
Published: July 2006

N-Sulfinylaniline reacted with nitrogen tetroxide to form the anhydrous benzenediazonium nitrate. The reactions of N-sulfinylaniline and several of its p-substituted derivatives with nitrosyl chloride also gave the anhydrous diazonium chlorides in the crystalline state. Aliphatic N-sulfinyl-amines reacted with nitrosyl chloride to form alkyl chlorides, probably by the decomposition of the initially-formed diazonium chlorides; during this reaction, no rearrangement of the alkyl group was observed.
Organic Sulfur Compounds. XI. The Reactions of the Cyclic Sulfites with the Aromatic Aldehydes
Authors: Kobayashi Michio , Yabe Akira , Kiritani Reiko
Published: July 2006

The reactions of the cyclic sulfites with aldehydes to give the cyclic acetals have been investigated with the stereochemical and with the 18O tracer technique. Both groups of evidence have indicated that the bonds broken are the S–O, not the C–O bond, of the sulfites.
Studies on Reactions of Polypropyrene. VI. The Thermal Degradation of Polypropylene Accelerated by the Fine Powdery Polymer with Closslinkage
Authors: Mizutani Yukio , Yamamoto Keiichi , Matsuoka Seishiro
Published: July 2006

The thermal degradation of polypropylene was investigated in the presence of the fine powdery polymer with crosslinkage by the use of an extruder under a nitrogen atmosphere. The fine powdery polymer was thus found to be effective as an accelerator for the thermal degradation of polypropylene. The fine powdery polymer used was prepared by the emulsion polymerization of some vinyl monomers and divinyl benzene or by the polymerization of glycidyl methacrylate and divinyl benzene in n-heptane. The fine powdery polymer consisting of glycidyl methacrylate and divinyl benzene was preferable to that with no reactive functional group, because of the reactivity of the glycidyl group. The polypropylene was modified and made dyeable by the thermal degradation accelerated by the fine powdery polymer.
The Syntheses of Polypyromellitimide-amides
Authors: Saga Motoo , Shono Toshiyuki , Shinra Koichiro
Published: July 2006

Dibasic acids containing a pyromellitimide ring were synthesized by the reaction of pyromel-litic dianhydride with such ω-aminoacids as glycine, ε-amino-caproic acid and p-amino-benzoic acid. By the condensation polymerization of the dibasic acids obtained above with diamines, polypyromellitimide-amides were synthesized. The polymers were soluble in m-cresol and sulfuric acid, and the inherent viscosities of the polymers ranged from 0.21 to 0.42 (in m-cresol). The polymers were found to be considerably heat-stable.
Studies on Amino-hexoses. IX. The N-Deacetylation of Methyl N-Acetyl-β-d-glucosaminide, Methyl N-Acetyl-3-O-methyl-α- and β-d-glucosaminide, and Methyl N-Acetyl-4,6-O-ethylidene-α-d-glcosaminide
Authors: Fujinaga Mamoru , Matsushima Yoshio
Published: July 2006

The efficiency of hydrazine as a mild N-deacetylating reagent has been studied in the reaction of hydrazine with four N-acetylaminosugars. This reagent has been shown to be of great use in the N-deacetylation of methyl N-acetyl-β-d-glucosaminide and methyl N-acetyl-4,6-O-ethylidene-α-d-glucosaminide. It may be noted that the 3-O-substitution of the sugars makes the deacetylation reaction reluctant. The synthesis of methyl N-acetyl-4,6-O-ethylidene-α-d-glucosaminide and the isolation of crystalline methyl β-d-glucosaminide and methyl 4,6-O-ethylidene-α-d-glucosaminide in the free-base form have been described.
Kinetic Studies of the Oxidation of Uranium Iodides by Oxygen
Authors: Handa Muneo
Published: July 2006

The kinetics of the oxidations of uranium tetraiodide and of triiodide by oxygen were studied over the temperature ranges from 55.0 to 66.5°C and from 88.5 to 103.5°C respectively. The experiments were carried out with an apparatus in which the column of a gas chromato-graph was replaced by an electric furance and traps of water vapor, oxygen and iodine. Most of the experiments were performed with the same partial pressure of oxygen (64 mmHg) and total flow rate (60 ml. per min.). The activation energies for the reaction of oxygen with uranium tetraiodide and triiodide were, respectively, 21.1 and 22.5 kcal. per mole. The rate of the formation of uranium trioxide was in agreement with the kinetics to be expected for reaction between a gas and a solid at a continuously diminishing spherical interface.
Correlations of the Structural Unit of Organic Compounds with the G Values of Thier Radiolytic Products
Authors: Isoya Toshiro , Hirota Kozo , Hatada Motoyoshi
Published: July 2006

Two correlations have been found between the G values of the radiolytic products and the number of the structural unit, n, in an organic molecule; (i) The G value from the homologous compounds has a linear relation to 1/n in the n≤m region and is independent of n in the n≥m region, where m is the number of the C–C bond through which the energy can be transferred, and (ii) the G(CH4) value from paraffin hydrocarbons, where the “terminal effect” is remarkable, has a linear relation to 1/n in both the n≥m and n≤m regions. These relations may be explained in terms of the energy transfer through C–C bonds.
The Constitution, Reactivity and Thermal Change of Phosphate Ores
Authors: Ando Jumpei , Matsuno Seiichi
Published: July 2006

Tests were made on twenty-five samples of phosphate ores from all over the world deposits. All of the samples consisted of apatite, plus small amounts of calcite and other minerals. The apatite crystals of the sedimentary ores ranged in size from around 0.05 μ (Gafsa, North Carolina, etc.) to around 0.5μ (Taiba), while those of igneous ores reached 100 μ. The difference between the ores in their reactivity with citric, hydrochloric and nitric acid was mainly due to the difference in crystal size. The decomposition of the ores by a mixture of sulfuric and phosphoric acids was seriously affected by the coating of calcium sulfate crystals on the surface of the ores, and also by the aluminum and iron present in the acids and ores. The lattice constant, a0, of the apatite of the ores ranged from 9.340 to 9.422 Å; it was generally smaller for the ores which had larger F2/P2O5 ratios. Upon calcination above 500°C, the a0 value of the apatite which had an excess of fluorine increased and approached that of true fluorapatite. The reactivity of the ores with the acids generally decreased upon calcination due to the sintering of the grains and the crystal growth. For ease of decomposition by a mixture of sulfuric and phosphoric acids, the calcined ore should contain a small amount of carbon dioxide. Tests also were made on the amount of organic matter and its decrease upon calcination.
Photochemical Reactions of Ethyl Chloroglyoxylate with Cyclohexane, Cyclohexene, and Toluene
Authors: Pac Chyongjin , Tsutsumi Shigeru
Published: July 2006

The photochemical reactions of ethyl chloroglyoxylate with cyclohexane, cyclohexene, and toluene have been carried out, and the reactivity of an alkyl radical towards ethyl chloroglyoxylate has been qualitatively discussed. A cyclohexyl radical attacks the carbonyl group of the acid chloride function in ethyl chloroglyoxylate to cause a chain reaction; cyclohexanecarbonyl chloride (51%) and ethyl cyclohexylglyoxylate (2—3%) are thus obtained, along with other minor products. On the other hand, a cyclohexen-3-yl or a benzyl radical might be unable to attack ethyl chloroglyoxylate under the conditions investigated.
The Synthesis of 5- and 6-Aminoazulene Derivatives from 5- and 6-Acetylazulene Derivatives
Authors: Nozoe Tetsuo , Takase Kahei , Tada Masao
Published: July 2006

The Schmidt reactions on diethyl 5-acetyl-2-aminoazulene-1, 3-dicarboxylate and diethyl 6-acetyl-2-aminoazulene-1, 3-dicarboxylate afforded diethyl 2, 5-diaminoazulene-1, 3-dicarboxylate(I) and diethyl 2, 6-diaminoazulene-1, 3-dicarboxylate respectively. A preferential formation of the 5-acetamido-2-amino compound upon the mild acetylation of I, which contrasted with the preferential diazotization of the 2-amino group, was observed.
The Reaction of Methylchlorodisilanes with t-Butyl Hydroperoxide
Authors: Kawazumi Kazuhisa , Murai Bunjiro
Published: July 2006

The authors wished to get two new organosilyl peroxides with a silicon-silicon linkage, t-butylperoxypentamethyldisilane [(CH3)3SiSi(CH3)2(OOC(CH3)3)] and 1, 2-di-t-butylperoxytetramethyldisilane [((CH3)3COO)(CH3)2SiSi(CH3)2(OOC(CH3)3)], by the reaction of the corresponding chlorodisilanes with t-butyl hydroperoxide. The reaction, however, did not give the desired product; rather, it led to the formation of t-butoxypentamethyldisiloxane [(CH3)3SiOSi(CH3)2-(OC(CH3)3)] and 1-t-butoxy-3-t-butylperoxytetramethyldisiloxane [((CH3)3CO)(CH3)2SiOSi-(CH3)2(OOC(CH3)3)] respectively, substances which are believed to have resulted from the intramolecular rearrangement of the desired peroxydisilanes.
Studies of Thio Acids. VI. The Electrolysis of Thiostearic Acid
Authors: Hirabayashi Yoshio , Mazume Tetsuro
Published: July 2006

Potassium thiostearate was electrolyzed in methanol in the presence of an excess of thiostearic acid by the use of platinum electrodes and a direct current. The product obtained by this electrolysis was found to consist of distearoyl disulfide, methyl stearate, stearic acid, and thiostearic acid. The mechanism of the formation of the above components was discussed in contrast with that of the Kolbe reaction of fatty acids.
The Synthesis of γ-Alkylamides of l-Glutamic Acid. The Reactions of Metallic Salts of l-Pyrrolidonecarboxylic Acid with Primary Alkylamines
Authors: Yamada Yoshitaka , Sakurai Moritaro , Tsuchiya Yoshio
Published: July 2006

l-Theanine, a principal component of flavors contained in green teas, and its homologs have been synthesized by the reactions of several metallic salts of l-pyrrolidonecarboxylic acid with primary alkylamines. Hitherto, γ-alkylamides of l-glutamic acid had been prepared in low yields by the reactions of l-pyrrolidonecarboxylic acid with anhydrous alkylamines. The use of metallic salts, especially cupric, zinc, and manganese salts, increased the yields of the γ-amides remarkably.
The Synthesis of dl-α-Dihydrocaranone and γ-Lycorane
Authors: Ueda Nasuo , Tokuyama Takashi , Sakan Takeo
Published: July 2006

dl-α-Dihydrocaranone (XII) has been synthesized stereoselectively, using the ring-closure reaction via benzyne intermediate of N-(2-bromo-4,5-methylenedioxybenzyl)octahydroindole-6-one (X) with lithium piperidide in tetrahydrofuran. dl-γ-Lycorane (III) has been obtained by the Hauptmann reduction of XII.
Studies of the Surface Oxide Layer of Platinum Electrode
Authors: Ohashi Kunio , Sasaki Kazuo , Nagaura Shigeo
Published: July 2006

The formation and reduction rates of the oxide layer of the platinum electrode were investigated by triangular-wave voltammetry and chronopotentiometry. A rate equation for the anodic process has been proposed in order to describe the fact that the electrode potential increases linearly with an increase in the surface concentration of oxygen. The cathodic reduction of surface oxide obeys the second-order rate law with respect to the amount of oxide covering the surface.
The Deterioration of Oxidative Polymerized Films
Authors: Chen Leo-Wang , Kumanotani Ju
Published: July 2006

The deterioration of oxidative polymerized films, such as films of polymerized oils, alkyd resins, and phenolic varnishes, was studied by means of dynamic-mechanical measurements, in addition to such conventional methods as infrared spectral and elementary analysis. The visco-elastic changes induced by thermo-oxidation were correlated with the network structure of the films. The baked films are more stable than the air-dried films. The aliphatic chains decomposed more easily when a comparison was made among air-dried film and baked film of alkyd resin modified by unsaturated fatty acid; this is because of the existence of more hydroperoxyl and conjugated carbonyl groups and the effect of the drying agent contained in the air-dried film. After thermo-oxidation, the glass-transition temperature and the degree of crosslinking of the film showed an increase, an increase which is considered to be the result of the oxidative decomposition and cross-linking of aliphatic chains. It was also observed that the impact strength of baked film decreased upon thermo-oxidation.
A Theoretical Interpretation of the Substituent Effects in Argentation Equilibria of Aromatic Hydrocarbons
Authors: Fueno Takayuki , Okuyama Tadashi , Furukawa Junji
Published: July 2006

The effects of ring substituents on the stability of silver ion complexes of benzene and styrene are discussed in terms of the delocalization energies as calculated by the simple LCAO MO method. It is demonstrated that the delocalization energy responsible for the formation of the σ -type molecular bond can predict the relative stabilities of the complexes; the calculated energies are linearly correlated with Hammett’s sigma values. The π-type molecular bond energy arising from the delocalization of silver d-electrons decreases linearly with the increase in the σ-type bond energy. In cases where the two energies are comparable in magnitude, the substituent effects may well be controlled by the entropy term, as has previously been demonstrated experimentally. This apparent paradox encountered in the interpretation of substituent effects may best be reconciled by assuming that the behavior of the silver 4d-orbital in complexation is more closely associated with the entropy change than that of the 5s-orbital of the same atom.
The Infrared and Raman Spectra of the Trimethylaluminum -Dimethyl Sulfide Complex
Authors: Tarao Ryokichi
Published: July 2006

The infrared and Raman spectra of a mixture of trimethylaluminum and dimethyl sulfide (molar ratio, 1 : 1) have been measured (IR: 3100–300 cm−1, Raman: 3100–130 cm−1). The spectra obtained are entirely different from the superposition of the spectra of the two components. Tentative assignments for most of the infrared bands and Raman lines have been suggested. The CS stretching vibration lines of dimethyl sulfide shift to frequencies lower by about 5 cm−1 when it is mixed with trimethylaluminum. These findings, together with the measurement of the Raman spectrum of the mixture in a 10-volume-percent benzene solution, indicate that the 1 : 1 mixture of trimethylaluminum and dimethyl sulfide forms a pure coordination complex, Al(CH3)3·(CH3)2S, which does not dissociate into its components appreciably in either the liquid state or the benzene solution.
The Direct Complexometric Titration of Thallium(III) Using Iron(III)-Sulfosalicylate Complex as Metal Indicator
Authors: Aggarwal R C , Srivastava A K
Published: July 2006

The iron(III)-sulfosalicylate complex has been used as the indicator for the direct complexometric determination of thallium(III). This indicator permits the rapid and accurate determination of both micro and macro quantities of thallium(III). The titrations are best carried out at about pH 2.6. Most of the divalent cations, such as calcium, strontium, barium, magnesium, manganese and mercury, and trivalent cations, such as chromium and aluminum, do not interfere in the determination.
Studies of Thio Acids. VIII. The Reaction of Thiostearic Acid with Alcohols
Authors: Hirabayashi Yoshio , Mizuta Masateru , Mazume Tetsuro
Published: July 2006

The products obtained by heating thiostearic acid in methanol, aqueous methanol, ethanol, or aqueous ethanol have been found to consist of hydrogen sulfide, distearoyl sulfide, methyl or ethyl stearate, thiostearic acid, and stearic acid, the last of which has been detected only in the case of aqueous alcohols. On the basis of the above results, the following scheme may be involved, at least in part, in the formation of carboxylic ester and hydrogen sulfide by heating the thio acid in alcohols:

(Remark: Graphics omitted.)
The Nitration and Halogenation of Palladium Acetylacetonate
Authors: Kasahara Akira , Uji-ie Katsuyasu , Tanaka Keiko
Published: July 2006

The pseudo-aromatic divalent palladium acetylacetonate has been found to undergo electrophilic substitution at the central carbon of the chelate ring. The mononitro (decomp.p. 240–245°C, λmax 325 mμ) and dinitro (decomp.p. 250–255°C, λmax 324 mμ) palladium acetylacetonates were prepared by treating palladium acetylacetonate with a mixture of copper nitrate trihydrate and acetic anhydride; they were characterized by their infrared and NMR spectra. The halogenation of palladium acetylacetonate was accomplished with N-halosuccinimides in chloroform. Dichloro (decomp.p. 205–210°C, λmax 345 mμ), dibromo (decomp.p. 240–245°C, λmax 345 mμ) and diiodo (decomp.p. 195–200°C, λmax 324 mμ) derivatives were isolated and characterized by their spectra.
Studies of Peptide Antibiotics. VI. Syntheses of Cyclic Penta and Decapeptides with a Glycyl-l-ornithyl-l-leucyl-d-phenylalanylglycyl Sequence
Authors: Kondo Michio , Aoyagi Haruhiko , Kato Tetsuo , Izumiya Nobuo
Published: July 2006

A cyclic decapetide dihydrochloride, cyclo-(glycyl-l-ornithyl-l-leucyl-d-phenylalanylglycyl)2·2HCl, which is an analog of gramicidin S, and a cyclic pentapetide monohydrochloride, cycloglycyl-l-ornithyl-l-leucyl-d-phenylalanylglycyl·HCl,where synthesized in order to compare their decapeptide active esters was found to yield the same cyclic bezyloxycarbonyl-substiuted decapetide: this was converted by hydrogenolysis to the cyclic decapeptide dihydrochloride mentioned above. The cyclization reaction of a linear pentapetide active ester, in which the glycines are both terminal amino acid residues, yielded a cyclic benzyloxycarbonyl-substiuted pentapetide exclusively. When another linear pentapeptide active ester and a pentapetide azide where also subjected to cyclization reaction, they afforded the same cyclic benzyloxycarbonylsubstituted pentapeptide; this was then hydrogenolyzed to the corresponding cyclic pentapeptide monohydrochloride. The effects of the two cyclic peptide hydrochlorides on the bacterial growth were tested; no retardation of growth was observed with any of the microorganisms tested.
The Reaction of p-Methoxystyrene-α-14C with Lead Tetraacetate
Authors: Yukawa Yasuhide , Hayashi Nobuyoshi
Published: July 2006

The reaction of p-methoxystyrene with lead tetraacetate in glacial acetic acid should proceed mainly through the rearrangement of the carbon skeleton. The possibility of the hydrogen migration can not be ruled out, but its extent should be only 7% even if it is involved.
The Reaction of Organodisilanes with N-Bromosuccinimide
Authors: Sakurai Hideki , Hosomi Akira , Nakajima Jun-ichi , Kumada Makoto
Published: July 2006

The reactions of three hexaorganodisilanes with N-bromosuccinimide in carbon tetrachloride or in chloroform were carried out. Hexamethyldisilane afforded trimethylbromosilane (82.9–100%) and N-trimethylsilylsuccinimide (73.5–79.5%). No bromomethylpentamethyldisilane was obtained. Similarly, 1,2-diphenyltetramethyldisilane gave phenyldimethylbromosilane and a small amount of bromobenzene. The N-silyl compound could not be isolated, but succinimide was obtained as a decomposition product. Phenylpentamethyldisilane gave trimethylbromosilane and phenyldimethylbromosilane in 67.4 and 12.3% yields respectively. A possible reaction mechanism was discussed.
The Reactions of Oximes with Lead Tetraacetate. The Scope of the Reactions
Authors: Yukawa Yasuhide , Sakai Mitsuru , Suzuki Shigeo
Published: July 2006

A detailed study of the reaction of oximes by lead tetraacetate has been made. It has beers found that the reaction gave nitrogen and the respective aldehydes or ketones in good yields.. In the reaction, which can be applied to general oximes, the order of yields was: aliphatic aldoximes >aliphatic ketoximes>alicyclic ketoximes >aromatic ketoximes>aromatic aldoximes. Some limited mechanistic implications are presented and discussed on the basis of the results obtained. Stoichiometrically, it has been found that 2 moles of oxime react with 1 mole of lead tetraacetate to produce 2 moles of aldehyde or ketone and 1 mole of nitrogen.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. XII. The Circular Dichroism of Hexose Nitrates
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko , Yamada Noriko
Published: July 2006

Circular dichroism has been measured of eighteen nitrates of hexoses (glucose, mannose and altrose), and its correlation with the rotatory dispersion as well as the ultraviolet absorption has been established, verifying even a number of suggestions made as regards the sign of some ambiguous Cotton effects (Tsuzuki et al., This Bulletin, 39, 1391 (1966)), which has eventually led to some significant conclusions.
Kinetic Studies of Ammonia Oxidation in Shock Waves. II. The Rate of Ammonia Consumption
Authors: Takeyama Tetsu , Miyama Hajime
Published: July 2006

An investigation was made of ammonia oxidation in shock waves at temperatures from 2100 to 2600°K by monitoring the ultraviolet absorption of ammonia at 2245 Å. The absorption coefficient of ammonia was measured at various temperatures; the rate constant of the decomposition reaction at higher temperatures with a mixture of 1% NH3 and 99% Ar was found to be in good agreement with the results of other studies. By using several mixtures of ammonia and oxygen highly diluted with argon, the rate of ammonia consumption immediately after an induction period was found to be expressed by:

−\left(\fracd[NH3]dt\ight)0=k0[NH3]1.5[O2]0.5[Ar]0.5

where: logk0(11.5mole−1.5sec−1)=12.77±0.10+(−8488±573)⁄T. This corresponds to an apparent activation energy of 38.8±2.6 kcal./mole.