bluuebunny/crossref_metadata_2025 huggingface dataset:
The Surface Activity of Tetrabutylammonium Halides in the Aqueous Solutions
Authors: Tamaki Kunio
Published: July 2006

The surface activity of the tetrabutylammonium halides at the air/aqueous solution interface or at the hexane/aqueous solution interface has been studied. The surface or inter facial tension versus the concentration curves of the electrolytes are markedly dependent on the kind of their counter-ions, just as with these electrolytes in aqueous solutions. The surface activity of tetrabutylammonium iodide is fairly strong; it approximately corresponds to that of the surface-active straight-chain electrolyte with an octyl group. From the thermodynamic parameters of the adsorption of tetrabutylammonium iodide, it is found that the standard free energy of adsorption becomes negative as a result of the large positive values of the standard entropy of adsorption, irrespective of the positive values of the standard enthalpy change. This suggests that the adsorption is a “hydrophobic” effect; that is, the “icebergs” around the nonpolar groups of the electrolyte return to the original water by the process of the transfer of the hydrophobic ions from the aqueous solution to the surface phase.
The Reaction of Tropones with Alkali and Amines in the Presence of the Copper Ammine Complex and Potassium Ferricyanide
Authors: Kikuchi Katsuo
Published: July 2006

The reaction of tropone and potassium hydroxide in the presence of potassium ferricyanide gave tropolone, salicylaldehyde, and p-hydroxybenzaldehyde, while in the presence of the copper ammine complex it afforded 2-aminotropone and salicylonitrile. Similarly, when tropone was reacted with aqueous ammonia, methylamine, or dimethylamine, 2-aminotropone and its N-methyl derivatives were formed. The reaction of 2-phenyltropone with ammonia and methylamine, and the reaction of 2-α-naphthyltropone and 4-bromo-2-phenyltropone with methylamine in the presence of copper salt, also afforded 2-aminotropone derivatives and/or salicylaldehyde derivatives.
A New Synthesis of Dialkoxymethane. The Magnetic Nonequivalence of Methylene Protons in Certain Dialkoxymethane
Authors: Sato Takeo , Saito Yoshitaka , Kainosho Masatsune , Hata Kazuo
Published: July 2006

Dimethyl sulfoxide (DMSO), under acidic conditions, is known to yield formaldehyde as one of its decomposition products. A new method of synthesizing dialkoxymethanes, which consists of the treatment of alcohols with a DMSO-PPA (polyphosphoric acid) mixture, has been shown to be convenient and also generally applicable. Under mild conditions, five primary alcohols and four secondary alcohols are converted to the corresponding formals in 50—80 and 30—40% yields respectively. Dimethyl disulfide, bis(methylthio) methane and methylthiomethyl ether and an oxidation product of the alcohol have been shown to be the main by-products in this reaction. The examination of the NMR spectra has revealed that the acetal methylene protons of dialkoxymethanes made from (±)-secondary alcohols are observed as an AB quartet and as a singlet, each arising from meso and racemic compounds, respectively.
Studies of Aminosugars. XIV. Syntheses of 6,6′-Diamino-6,6′-dideoxymaltosylamine, 1′,6,6′-Triamino-,1′,6,6′-trideoxysucrose and 6,6′-Diamino-6,6′-dideoxytrehalose
Authors: Umezawa Sumio , Tsuchiya Tsutomu , Nakada Saburo , Tatsuta Kuniaki
Published: July 2006

Several aminodisaccharides have been synthesized for the investigation of the relationship between the structural and biochemical characteristics of aminoglycosides. The preferential tosylation of maltose, followed by acetylation and bromination, yielded 2,2′,3,3′,4′-penta-O-acetyl-6,6′-di-O-tosylmaltosyl bromide, of which the bromine atom and the two tosyloxy groups were replaced by azido groups. The removal of acetyl groups and the catalytic hydrogenation of the azido groups gave 6,6′-diamino-6,6′-dideoxymaltosylamine. By an analogous procedure, 1′,6,6′-triamino-1′,6,6′-trideoxysucrose was prepared from sucrose via 2,2′,3,3′, 4,4′-penta-O-acetyl-1′,6,6′-triazido-1’,6,6′-trideoxysucrose. 6,6′-Diamino-6,6′-dideoxytrehalose was obtained by the ammonolysis of 2,2′,3,3′,4,4′-hexa-O-acetyl-6,6′-di-O-tosyltrehalose.
Studies of the Interaction of Sodium Polyphosphates with Acridine Orange
Authors: Miura Masaji , Kubota Yukio
Published: July 2006

The interaction of sodium polyphosphates with acridine orange has been studied by means of absorption spectra, fluorescence, and viscosity measurements. Polyphosphates with a variety of molecular weights were used in order to investigate the effect of the degree of polymerization (\barn) on the interaction. No spectral change was observed in the case of polyphosphates with \barn<5. In the case of \barn=9, an absorption band corresponding to the dye dimer was observed, whereas in the case of larger \barn values those corresponding to higher aggregates were also found. The maximum metachromasy occurred at P⁄D=3–6. Fluorescence quenching was observed, accompanied by an absorption change. Such behavior may be considered to be characteristic of the dye molecules bound to the long-chain polyphosphates; the bound-dye molecules seem to exhibit almost no fluorescence. The quenching constants of the fluorescence increased with the increase in \barn values. The binding energies were estimated to be 5–6 kcal/mol independent of the \barn values. In the presence of acridine orange, the reduced viscosity of Kurrol’s salt decreased remarkably, probably as a result of the neutralization of the charged phosphate groups. Further, its reduced viscosity decreased remarkably with time; this may be attributed to the catalytic action of the dye on the hydrolytic degradation of polyphosphates.
The Crystal Structure and the Absolute Configuration of (+)-2-Benzylglutamic Acid Hydrobromide Dihydrate
Authors: Ashida Tamaichi , Sasada Yoshio , Kakudo Masao
Published: July 2006

The crystal structure of (+)-2-benzylglutamic acid hydrobromide dihydrate has been determined using three-dimensional X-ray intensity data. The crystal is orthorhombic, with four formula units in a unit cell with the dimensions: a=8.38, b=10.54, and c=17.68 Å, the space group being P212121. The structure was solved by the heavy atom method, and its parameters were refined by the least-squares method using anisotropic thermal parameters, the final R being 0.073. The absolute configuration of the glutamic acid has also been determined to be d-(+)-2-benzylglutamic acid, [α]d20+1.65° (c 10, 4 n HCl). The conformation of the carbon skeleton of the glutamic acid is different from any of the glutamic acids so far analyzed, due to the internal rotations of the C–C bonds. A detailed comparison of the conformations of several glutamic acids and glutamines will be given. Nine independent hydrogen bonds make a rather unique and complicated three-dimensional network. Among these, two between the carboxyl groups (donor) and the water molecules (acceptor) are found to be fairly strong, their bond lengths being 2.55 and 2.51 Å.
Solvent Effects on the Absorption and Emission Spectra of p-Aminoacetophenone
Authors: Yamaguchi Gentaro , Kakinoki Yoshiaki , Tsubomura Hiroshi
Published: July 2006

The absorption and emission spectra of p-aminoacetophenone (PAAP) were measured in various solvents at different temperatures. Several interesting facts have been revealed: PAAP, which is non-fluorescent in other solvents, fluorescences strongly in the ethanol matrix at 77°K; the ratio of the intensity of fluorescence to that of phosphorescence varies according to the wavelength of the exciting light; the phosphorescence band shifts largely by changing the temperature. Explanations for these observed results have been given by considering that the lowest 1(π→π*) level and the 1(n→π*) level lie fairly close to each other in this molecule and a reversal of the energy levels occurs by changing the solvent and the temperature. The lowest triplet state of PAAP is concluded to be 3(π→π*) and not 3(n→π*).
The Solubility of Hydrogen Chloride in Volcanic Rock Melts at a Total Pressure of One Atmosphere and at Temperatures of 1200°C and 1290°C under Anhydrous Conditions
Authors: Iwasaki Bunji , Katsura Takashi
Published: July 2006

The solubility of hydrogen chloride in volcanic rock melts was experimentally determined at temperatures of 1200°C and 1290°C with the variation in the partial pressure of hydrogen chloride mixed with nitrogen under one atmosphere. The solubility of hydrogen chloride decreases not only with a rise in the temperature, but also with an increase in the silica content of volcanic rock melts, while it increases with an increase in the partial pressure of hydrogen chloride. The equilibrated concentration of chlorine obtained by experiments was compared with those in natural basalts collected from Japan and Hawaii.
A New Spectrophotometric Method for the Determination of Micro Amounts of Thiocyanate by Solvent Extraction
Authors: Koh Tomozo , Iwasaki Iwaji
Published: July 2006

A study was made aimed at devising a new spectrophotometric method for the determination of ultramicro amounts of thiocyanate. A methylene blue is slightly extracted into a dichlo-roethane layer from an acid aqueous solution. However, if methylene blue is added to an acid aqueous solution containing thiocyanate, the complex formed in a 1 : 1 ratio between methylene blue and thiocyanate is well extracted into dichloroethane, the amount of extraction being proportional to the amount of thiocyanate present. Thiocyanate is determined by measuring the absorbancy of the dichloroethane solution of the complex at the wavelength of 657 mμ. This method is suitable for the determination of thiocyanate within the concentration range from 2.0×10−7 to 6.0×10−6  m by employing a 5.0-ml portion of dichloroethane for extraction, and in the range from 3.0×10−7 to 1.0×10−5  m by employing a 10.0-ml portion of it.
Hydrocarbons in Patchouli Oil
Authors: Tsubaki Naoko , Nishimura Kiichi , Hirose Yoshio
Published: July 2006

An analytical study of patchouli oil was carried out, and the following compounds were identified; α- and β-pinene, limonene, camphene, β-elemene, caryophyllene, α- and β-patchoulene, α-guaiene, α-bulnesene, allo-aromadendrene, and α-gurjunene. The last six hydrocarbons were hydrogenated in order to complete the identification and to ascertain their spatial configurations by correlating the saturated skeletons with each of these or with known ones.
On the Mechanism of the Reaction of Sodium-Lead Alloys with Ethyl Halides
Authors: Mishima Shigeji
Published: July 2006

The reactivities of ethyl halides with active lead or sodium were investigated. The reactivities of ethyl halides with sodium-lead alloys were quite analogous to those of ethyl halides with sodium. The analysis of the gases produced in the reaction of sodium-lead alloys with ethyl halides revealed the presence of ethane, somewhat smaller amounts of ethylene and propane, etc. In the reaction of a sodium-lead alloy with ethyl halide in the presence of isopropylbenzene, 2, 3-dimethyl-2, 3-diphenylbutane was formed. In the reaction of ethyl bromide or ethyl iodide with sodium dispersed in isopropylbenzene, 2, 3-dimethyl-2, 3-diphenylbutane was also formed. On the basis of these results, it may be concluded that, in the reaction of sodium-lead alloys with ethyl halides, the initial step in the reaction is the formation of ethyl radicals by the reaction of ethyl halides with sodium in the alloys; then these radicals are combined with lead.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. XIII. Alkylxanthates of Glucose
Authors: Tsuzuki Yojiro , Tanabe Koko , Akagi Masuo , Tejima Setsuzo
Published: July 2006

The rotatory dispersions and ultraviolet absorption spectra of six homologs of 2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl alkylxanthates have been measured, and the effects of the alkyl groups on the rotatory dispersion have been discussed by comparison with the case of the sugar xanthates already studied by Tsuzuki et al. (Bull. Chem. Soc. Japan, 37, 162, 730 (1964)). All show positive Cotton effects, the molecular amplitude of which diminishes with an increase in the number of carbon atoms of the alkyl group, while the molecular extinction coefficient decreases as the carbon number of the alkyl group increases from 1 to 4. These facts agree with the earlier findings and can be interpreted in terms of the relation, R=μcosθ\sqrtD, between the electron transition, the rotational strength, and the dipole strength given by S. F. Mason (Quart. Rev., 17, 20 (1963)).
Studies of Purine N-Oxides. II. The Reaction of Hypoxanthine 1-N-Oxide and 2′,3′,5′-Tri-O-acetylinosine 1-N-Oxide with Phosphoryl Chloride
Authors: Kawashima Hideaki , Kumashiro Izumi
Published: July 2006

Hypoxanthine 1-N-oxide was treated with phosphoryl chloride in the presence of organic bases to give 2,6-dichloropurine. Adenosine 1-N-oxide was converted to inosine 1-N-oxide by deamination with nitrous acid. Inosine 1-N-oxide was acetylated with acetic anhydride in pyridine to yield 2′,3′,5′-tri-O-acetylinosine 1-N-oxide. The latter compound was similarly converted to 9-(2′,3′,5′-tri-O-acetyl-β-d-ribofuranosyl)-2,6-dichloropurine by treating it with phosphoryl chloride in the presence of organic bases.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. III. An Unexpected Side-reaction during the Synthesis of t-Amyloxycarbonylamino Acids
Authors: Sakakibara Shumpei , Itoh Masumi
Published: July 2006

Formation of unexpected by-products was observed when t-amyloxycarbonyl-(AOC) amino acid esters were prepared according to the previously published method from some specific amino acid esters using AOC-chloride as the reagent. Further, it was observed that the weaker the basicity of the amino acid ester used, the more by-product was formed under the same conditions. Analyses of the infrared and NMR spectra of the by-products revealed their structures to be ureid-type compounds of the respective amino acid esters. Use of excess AOC-chloride together with triethylamine was found to be the main cause of the ureid-formation, and the side-reaction could be almost entirely suppressed by the use of N, N-diethylglycine ethyl ester in place of triethylamine.
The Addition Reactions of Ethanol to Ethylene Induced by Gamma-ray Irradiation in the Gaseous Phase. I. Results and the Reaction Mechanisms
Authors: Hotta Hiroshi , Kurihara Hirondo , Abe Toshihiko
Published: July 2006

In the reaction named in the title, the major products of the reactions in the gaseous phase were 2-alkanols, 3-methyl-3-alkanols and 2-ketones, while low hydrocarbons were found only at temperatures higher than about 150°C. The reactions in the liquid phase, carried out at 100°C, did not give 2-ketones. The following conclusions were obtained by the analysis of the results. The major primary precursor is 1-hydroxyethyl radical. The radicals produced by its addition to ethylene, CH3–CH(OH)–(CH2)2n, give not only 2-alkanols but also radicals, CH3–C(OH)–(CH2)2n−1–CH3, as a result of rearrangement by the intramolecular hydrogen transfer. Some of the latter radicals act as precursors of 3-methyl-3-alkanols by their addition to ethylene, while the rest of the radicals give 2-ketones by hydrogen abstraction by ethylene. The latter reaction gives the ethyl radical, which is the precursor of various hydrocarbons. The intramolecular hydrogen transfer occurs even in the liquid phase to give 3-methyl-3-alkanols, but the rearranged radicals can give 2-ketones only in the gaseous phase.
Photoreduction of Proflavine in the Aqueous Solution. I. A Flash Photolysis Study
Authors: Kikuchi Kôichi , Koizumi Masao
Published: July 2006

The photoreduction of proflavine (D) in an aqueous solution at pH 4, was investigated by a flash technique. No intermediates were observed other than the triplet state (T) and the-semiquinone (DH·). This, with the finding that the triplet state decays according to the second order, rules out the occurrence of such reactions as T+D→D++D−, T+T→D++D−. In the presence of a large quantity of allylthiourea (RH2), the yield of leuco-proflavine (DH2) by one flash becomes constant independent of the ATU concentration, and its value is about one half of the yield of T. This indicates that almost all the T produced reacts with ATU. The rate constants obtained are:

T+T→ k3=0.8–1.4×109 m−1 sec−1

T→D k4\lesssim6×103 sec−1

T+RH2→DH·+RH· k5=4.3×106 m−1 sec−1

DH·+DH·→DH2+D k6=7×108 m−1 sec−1

T+O2→D+O2  k7=1.5–4.7×109 m−1 sec−1

DH·+O2→D+HO2· k8=1–3×109 m−1sec−1

m-Phenylenediamine was found to produce an intermediate which decays according to the first order. Its decay constant is 1.5×102sec−1. The rate constant for the reaction of T with m-phenylenediamine is 3.5×106  m−1 sec−1, about 1000 times smaller than that of the encounter-controlled process. This suggests that some of the rate constants reported by Oster should be reinvestigated.
The Crystal and Molecular Structure of the Tricyclic Methyldisilanylenesiloxane, ((CH3)6Si4O3)2
Authors: Higuchi Taiichi , Shimada Akira
Published: July 2006

Tricyclic methyldisilanylenesiloxane, ((CH3)6Si4O3)2, crystallizes in the triclinic space group P\bar1 with the unit-cell dimensions a=7.71, b=10.17, c=10.17 Å, α=106.7°, β=109.6° and γ=78.1° (Dx=1.165 g·cm−3 with Z=1 and Dm=1.12g·cm−3). The phase problem was mainly solved by the Patterson function. The final atomic parameters were obtained by the least-squares refinement. The molecule consists of two seven-membered rings and one six-membered ring in the chair conformation with a center of symmetry, and the skeletons of those rings consist of Si–Si and Si–O bonds. The seven-membered ring is nearly planar, except for one oxygen atom. The six-membered ring has a chair form. The dihedral angle between these rings is about 109°. The whole molecule, approximately, has a non-crystallographic mirror plane perpendicular to the line connecting the mid-points of two Si–Si bonds in the six-membered ring. The lengths of the Si–Si bonds are 2.36 Å and 2.38 Å with e. s. d. 0.01 Å. The mean lengths of the Si–O bonds and the Si–C bonds are 1.65 Å and 1.91 Å respectively. The Si–O–Si bond angles are 148° for the seven-membered ring, and 133° for the six-membered ring. Most of the closest contacts between the molecules are either of the CH3···CH3 type or of the CH3···O type.
The Crystal and Molecular Structure of 2-Bromomethyl-2,3-dihydrofuro[2,3-b]tropone
Authors: Shimanouchi Hirotaka , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao , Murata Ichiro , Kitahara Yoshio
Published: July 2006

Crystals of 2-bromomethyl-2,3-dihydrofuro[2, 3-b]tropone, C10H9O2Br, are monoclinic, with four molecules in a unit cell of the dimensions: a=8.34, b=10.23, c=11.26 Å, and β=96.9°, and with the space group of P21⁄c. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually against a standard scale. The structure was solved by the heavy atom method. The positional and thermal parameters were refined by the least-squares method. The final R factor for (hkl) reflections is 0.095. An apparent bond alternation in the conjugated seven-membered ring is observed. The longest and the shortest bond lengths in the ring are 1.48 and 1.36 Å respectively. The C–O bond length in the carbonyl group is 1.23 Å, suggesting a considerable contribution of ionic resonance forms. The IR absorption band at 1612 cm−1 could be assigned to the stretching frequency of the carbonyl group. The seven carbon atoms in the tropone ring are coplanar, but the oxygen atom in the carbonyl group lies significantly out of the seven-membered ring plane. This may be interpreted as a result of short intermolecular contact. The other intermolecular distances are equal to or larger than the sum of the van der Waals radii.
Studies on Pentakisantipyrine Copper(II) Perchlorate
Authors: Gopalakrishnan J , Ravi A , Patel C C
Published: July 2006

Five coordinated antipyrine (A) complex of copper(II) perchlorate, [CuA5](ClO4)2 has been prepared. Both the electric conductivity and the cryoscopic determination of molecular weight in nitrobenzene solution show that the complex dissociates into three ions. Differential thermal analysis gives one peak at about 285°C owing to the explosion of the complex. Infrared spectrum reveals the presence of both strongly and weakly coordinated antipyrine molecules in the complex. The complex in 1,2-dichloroethane absorbs at 16130 (ε=51) cm 15630 (ε=53) and 14500 (ε=56) cm1. These d-d transitions with comparatively high intensities suggest C4v symmetry for the complex ion [CuA5]2+. A square pyramidal structure with four antipyrine molecules in the square plane at normal Cu-O bond distance and one antipyrine occupying the axial position with an elongated Cu-O bond, is assigned to the complex ion.
The Photoinduced Isomerization of cis-Dichlorobis(ethylenediamine)cobalt(III) Chloride in Methanol
Authors: Kawaguchi Shinichi , Fujioka Hiroaki
Published: July 2006

The isomerization of cis-dichlorobis(ethylenediamine)cobalt(III) chloride to its trans form is induced at 0°C in methanol by ultraviolet irradiation. The visible light in the wavelength region of the ligand field bands is not effective, but the ultraviolet light corresponding to the charge transfer band is essential. The effects of the dissolved oxygen, the initial concentration of the reactant, and the intensity of the incident light were examined, and the reaction was found to proceed further even after the cessation of irradiation. A chain mechanism is proposed which includes the Co(II) species, the photoreduction product of the Co(III) complex, as a chain carrier. The isomerization reaction was also conducted at 0°C in the dark in the presence of cobalt(II) chloride and ethylenediamine; the most effective catalyst was assumed to be a five-coordinated Co(II) species, CoClen2+ . The induction period which was observed in the photoreaction was explained as being due to the deactivation of the reactive Co(II) species throguh oxidation with the dissolved oxygen.
Association Involving Optically Active Ions. I. Association Constants of Tris(ethylenediamine)cobalt(III) and Tartrate Ions
Authors: Ogino Kazuko , Saito Umihiko
Published: July 2006

The enantiomer differentiation of an optically active metal complex through the presence of another kind of optically active ion in the solution is considered to be due to association. A mathematical treatment has been made of the equilibria which exist in solutions containing either or both antipodes of an optically active ion and optically active counter ions which do not racemize rapidly. The results have been applied to a system of [Co en3]3+ (en=ethylenediamine) and d-tartrate ions. The increase in the optical absorbancy of [Co en3]3+ in the charge transfer absorption region is not the same for d-, l- and dl-[Co en3]3+. The association constants of d-[Co en3]3+·d-tartrate2− and l-[Co en3]3+·d-tartrate2 were found, by an analysis of the increase in the optical absorbancy, to be 26 and 21 respectively at μ=0.1 at 25°C.
The Kinetics of Substitution Reactions Involving Metal Complexes. IX. Reactions between Copper(II) and Propylenediaminetetraacetatoplumbate(II) and between Lead(II) and Propylenediaminetetraacetatozincate(II)
Authors: Ogino Hiroshi , Tanaka Nobuyuki
Published: July 2006

Kinetic studies of the reactions between copper(II) and propylenediaminetetraacetatoplumbate(II) and between lead(II) and propylenediaminetetraacetatozincate(II) have been carried out. It was revealed from these studies that the reactions proceed through four simultaneous reaction paths, of which two involve electrophilic substitution reactions and the others, the complex-forming reactions between entering metal ions and ligands dissociated from complexes. The rate constants were compared with those of the corresponding reactions involving metalethylenediaminetetraacetate and the effects of ligands on the reaction rates were discussed.
The Chemiluminescence of Luminol and Acetyl-luminol
Authors: Omote Yoshimori , Miyake Takeo , Ohmori Seiya , Sugiyama Noboru
Published: July 2006

Several acetyl derivatives of luminol were synthesized and their chemiluminescence were studied in water or in DMF-water. The role of the amino group in the chemiluminescence was revealed by comparing the chemiluminescence of luminol (I) with that of N-acetyl-luminol (II). Also, it was found that, in the case of the chemiluminescence of I or II in water, the emitting species did not seem to be the corresponding substituted phthalate ion, while in the case of the chemiluminescence in DMF-water, the 3-aminophthalate or 3-acetylaminophthalate ion could be presumed to be the emitting species.
The Hydrodimerization of Acrylonitrile
Authors: Misono Akira , Uchida Yasuzo , Tamai Katsumi , Hidai Masanobu
Published: July 2006

During the course of our studies of the dimerization of such vinyl monomers as acrylonitrile or acrolein with various Ziegler-type catalysts or metal carbonyls, it has been found that acrylonitrile is converted at an elevated temperature in an iron or cobalt carbonyl-alkali-water system, an iron or cobalt carbonyl-sodium borohydride or -lithium aluminum hydride system, or a cobalt carbonyl - H2 system to hydrodimers of acrylonitrile composed of adiponitrile and 2-methylglutaronitrile as well as propionitrile. Some iron carbonyl hydrides, which are presumably formed as intermediates in these reactions, were therefore prepared and subjected to reaction with acrylonitrile, 3-chloropropionitrile, or ethyl acrylate. On the basis of these experimental results, a reaction mechanism containing a cyanoethyl complex as an intermediate was proposed for the formation of hydrodimers of acryionitrile.
Studies on the Chemical Constitution of Agar-agar. XXIII. Isolation of d-Xylose, 6-O-Methyl-d-galactose, 4-O-Methyl-l-galactose and O-Methylpentose
Authors: Araki Choji , Arai Kiyoshi , Hirase Susumu
Published: July 2006

Commercial agar was subjected to complete hydrolysis with dilute sulfuric acid, and the products were carefully investigated. Besides d- and l-galactose, which have been known to exist, there were isolated small amounts of d-xylose, 6-O-methyl-d-galactose, 4-O-methyl-l-galactose, and O-methylpentose, all the sugars except the last one being obtained in crystalline forms. Among these products, 4-O-methyl-l-galactose is a new compound, so its structure has been fully investigated. As commercial agar is made from Gelidium amansii, occasionally mixed with several other species of seaweeds, the experiments were repeated for the agar prepared from G. amansii only. The same products as those from commercial agar were isolated except the O-methylpentose.
The S. W. Polarographic Determination of Disulfide, Mercaptan and Free Sulfur in Petroleum Naphtha
Authors: Kashiki Masayuki , Ishida Kazuyoshi
Published: July 2006

The application of square-wave polarography to the determination of small amounts of disulfide, mercaptan and free sulfur in a mixed solution of methanol, glacial acetic acid, and sodium acetate was studied. Disulfide, mercaptan, and free sulfur in concentrations below 10 ppm were easily determined in these mixed solvents. The derivative wave heights were proportional to the concentrations predicted by the theory of s. w. polarography. The effects of changes in solvent and in supporting electrolyte concentration, dissolved oxygen, and temperature were discussed. It was determined that concentrations of 2 vol% glacial acetic acid and 1.4 m sodium acetate were necessary to obtain a constant peak height. The temperature coefficients of disulfide, mercaptan and free sulfur were about 4.5 (first wave), 0.7 and 4.5% per degree respectively in the neighborhood of 25°C. The effect of the dissolved oxygen was removed by passing nitrogen through for 5 min.
Thermal Rearrangement of Mixed Dithiocarbamic-Imidic Anhydrides
Authors: Miyazaki Koshin
Published: July 2006

The various mixed dithiocarbamic-imidic anhydrides with the formula R2N–C(=S)–S–C-(=N–Ph)–Ph (I) rearranged to thiobenzoyl-thioureas with the formula R2N–C(=S)–N(–Ph)–C(=S)–Ph (II) when kept at an elevated temperature in an inert solvent. This rearrangement was found to be reversible, and it followed first-order kinetics. The value of the forward rate constant (k1) in o-dichlorobenzene at 100°C increased in the order: R=CH3>C2H5>n-C3H7>n-C4H9, and a good correlation between log k1 and σ* for R was obtained. The rearrangement following mixture of (CH3)2N–C(=S)–S–C(=N–Ph)–Ph and (C2H5)2N–C(=S)–S–C(=N–C6H5Cl-p)–Ph gave no crossed products. A probable reaction mechanism was proposed.
Reaction of Aluminum Haloalkoxide with Diazomethane
Authors: Saegusa Takeo , Tomita Shimpei , Ueshima Takashi
Published: July 2006

In the reaction of diazomethane with four aluminum haloalkoxides, Al(OCH2CF3)3 (I), Al(OCH2CCl3)3 (II), Al(OCH2CBr3)3 (III), and Al[OCH(CH2Cl)2]3 (IV), a methylene insertion into the aluminum-alkoxyl linkage was observed along with the polymethylene formation. By the methylene insertion, an organoaluminum compound with a haloalkoxymethyl-aluminum linkage is formed. Among aluminum alkoxides, these four haloalkoxides are distinguished by this methylene insertion. The usual aluminum alkoxides of unsubstituted alcohols do not undergo a methylene insertion reaction, but only the polymethylene formation. The difference in the reactivity towards diazomethane between the four haloalkoxides and usual alkoxides has been explained by the difference in acid strength.
Reduction Product and Leuco-form of Flavanthrone
Authors: Aoki Junji
Published: July 2006

By reducing flavanthrone (II), 8,16-diazapyranthrene (V) (denoted as flavanthrene) was obtained. On the other hand, leucoflavanthrone dibenzoate was also prepared. Since these two substanses give nearly identical absorption spectra, the leucobenzoate is considered to have the VI formula (5,13-dibenzoyloxy-8,16-diazapyranthrene) and to belong to the same conjugated system as flavanthrene. Consequently, it may be considered that the leuco-form of flavanthrone corresponds to the IV formula (5,13-dihydroxy-8,16-diazapyranthrene) in which two carbonyl groups are reduced, but not the III formula (8-hydro-13-hydroxy-5-oxo-8,16-diazapyranthrene) previously presented. In addition, the leucobenzoate can also be synthesized by boiling the quinone with zinc dust and benzoyl chloride in o-dichlorobenzene containing pyridine. This method, devised by the author, is easy to perform and gives a good yield.
Diphenyl Sulphoxide Complexes of Lanthanide and Yttrium Perchlorates
Authors: Ramalingam S K , Soundararajan S
Published: July 2006

Diphenyl sulphoxide complexes of nine lanthanide perchlorates of the general composition [Ln(DPSO)6](ClO4)3 where Ln=La, Ce, Pr, Nd, Sm, Gd, Ho and Yb and Y have been synthesised and characterized. Infrared studies indicate coordination through the oxygen atom of the ligand and the retention of the Td symmetry of the perchlorate group. The molar conductance and cryoscopic studies suggest a coordination number of six for the metal ions. Cryo-scopic studies in DMSO indicate that DMSO is a better donor than DPSO. DTA and UV data are also presented.
Hydrogen Formation in the Radiolysis of Liquid Olefins. The Role of Hot Hydrogen Atoms and Superexcited States
Authors: Hatano Yoshihiko , Shida Shoji , Sato Shin
Published: July 2006

The γ-radiolysis of liquid olefins was undertaken to obtain reliable evidence for a possible role of hot hydrogen atoms and superexcited states in radiation chemistry. The contribution of thermal hydrogen atoms may reasonably be excluded in this system. The effect of various electron or positive-ion scavengers on hydrogen formation in the radiolyses of liquid propylene and ethylene has been examined. The hydrogen formation is not appreciably affected by these additives, which indicates ionic species may not play an important role in the hydrogen formation. The liquidphase radiolyses of C3H6-C3D6 and C2H4-C2D4 mixtures have also been investigated and compared with those previously reported of C4H8-l - C4D8-l and trans-C4H8 - 2-trans-C4D8-2 mixtures. The data indicate that the hydrogen from the olefins except ethylene may be formed for the most part by bimolecular processes. A large part of the hydrogen from liquid ethylene may be interpreted in terms of the molecular detachment of a hydrogen molecule, while from the other olefins it may be interpreted in terms of the hydrogen-atom abstraction reaction of hot hydrogen atoms formed by direct excitation which must at least partially involve superexcitation. To attempt quantitative substantiation of the above viewpoint a simple calculation has been made based on the so-called optical approximation. Calculated yields of the hydrogen formation are apparently in good agreement with observed ones.
Formation Constants of Maleatochromium(III) Complexes and Some Properties Thereof in the Solid State
Authors: Tomita Takeshi , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The formation constants of the chromium(III) complexes with maleic acid have been determined by the pH method to be logk1=5.4±0.1, logk2=3.0±0.1, and logk3=1.9±0.2 at an ionic strength of μ=0.1 and at 25°C. We also attempted to prepare the solid of the chromium(III) complex with maleic acid. Though it was an amorphous solid to X-ray diffraction measurement, its composition was presumed to be [Cr(mal)(OH)(H2O)3]. After it had been dried in a desiccator for a few days, when it was exposed to moist air we observed the curious phenomenon that the solid was made jumping due to the absorption of water vapor.
Kinetics of Isotopic Exchange between 8-Quinolinol-14C and Tris-8-quinolinolato Complexes of Tervalent Typical Elements
Authors: Saito Kazuo , Takahashi Michihiko , Miyakawa Yukio , Masuda Kazuyo
Published: July 2006

Rate of isotopic exchange between 8-quinolinol-14C and the 8-quinolinolato (oxinato) complexes of aluminum, gallium and indium has been studied in chloroform. Pure yellow complexes are precipitated by adding petroleum ether to the reaction mixture. The exchange rate decreased in the sequence In>Al>Ga, and a detailed kinetic study can be substantiated only with the gallium complex below 0°C. The rate is proportional to the concentration of the complex, but is independent of that of free 8-quinolinol (quinolH) and the Arrhenius activation energy is 18 kcal per mole. The reaction is accelerated by acid and presumably by water. It appears as if one of the ligands is present as unidentate under the given condition and the break of the remaining bond would be the rate determining step. Any reagent that can retard the recombination of the free end of unidentate ligand would catalyse the exchange reaction.
Kinetics and Mechanisms of Thermal Decomposition Reactions of Cobalt(III) Complexes. Hexammine-, Halogenoammine- and Oxalatoamminecobalt(III) Complexes
Authors: Tanaka Nobuyuki , Nagase Kenzo , Nagakura Saburo
Published: July 2006

Kinetics of the thermal decomposition reactions of hexammme-,halogenoammine- and oxalatoamminecobalt(III) complexes in solid state has been studied by following the change in the cobalt (III) contents with time. It was found that the decomposition of these complexes was initiated by the change of the valence state of cobalt(III) to cobalt(II), and that these electrontransfer reactions were kinetically of a first order. The first-order rate constants, the activation energies and the frequency factors of these electron-transfer reactions were obtained. The values of the activation energies were found to increase in parallel with the increase in the difference between t2g and eg orbitals of the cobalt(III) complexes investigated. (The notations, t2g and eg, are used in the expression of an Oh-symmetry approximation for halogenoammine- and oxalatoamminecobalt(III) complexes.)
Activity Measurements in Orthosilicate and Metasilicate Solid Solutions. I. Mg2SiO4-Fe2SiO4 and MgSiO3-FeSiO3 at 1204°C
Authors: Kitayama Kenzo , Katsura Takashi
Published: July 2006

The activity-composition relations in ortho-, and metasilicate solid solutions in the FeO-MgO-SiO2 system are determined at 1204°C on the basis of the measurement of equilibrium oxygen partial pressures. Both the olivine and the pyroxene solid solutions show significant deviations from ideality. Using the present data, the standard free energy change of formation of ferrosilite (hypothetical compound, FeSiO3) is calculated to be −41.7±0.2 kcal/mol on the basis of the equilibrium between metallic iron and silica, and to be −1.6±0.2 kcal/mol on the wüstite (“FeO”) and silica.
Polymerization Catalyst of the Triethylaluminum-Chloral Hydrate System. I. Triethylaluminum-Chloral Hydrate Reaction and Catalyst Activity in Cationic Polymerization
Authors: Saegusa Takeo , Fujii Hiroyasu , Ueshima Takashi , Tanaka Katsumi
Published: July 2006

In reaction of AlEt3 with chloral hydrate has been investigated. The reaction system was examined by means of infrared and NMR spectra and by the vapor-phase chromatographic analysis of the acidolysis product of this system. The gas evolved during the reaction was also analyzed. The AlEt3-chloral hydrate system was proved to contain the linkages of >AlOCH2CCl3, >AlOCH(CCl3)OAl<, >AlOCH(Et)CCl3, >AlOAl<, >Al–Et and >Al–Cl. This system showed a very high catalytic activity for the cationic polymerization of i-butyl vinyl ether. Tetrahydrofuran, 3,3-bis(chloromethyl)oxacyclobutane, α-methylstyrene, and styrene were also polymerized by this catalytic system. The acid strength of the AlEt3-chloral [hydrate system was examined by two methods, the Hammett indicator method and shift of the infrared carbonyl band of xanthone caused by coordination to Lewis acid. It has been shown that the acid strength of this system is as strong as AlEt3–H2O (1:0.8) and Et2AlCl. The relation between the strong acid character of the AlEt3-chloral hydrate system and its structure was discussed.
Preparation and Properties of Aluminum and Zinc Haloalcoholates
Authors: Ueshima Takashi , Tomita Shimpei , Saegusa Takeo
Published: July 2006

Seven haloalcoholates of aluminum and zinc were prepared by the reactions of haloalcohols with metal alky Is in ethyl ether, and their properties were examined. The following differences have been observed between these haloalcoholates and the usual alcoholates, those with no halogen in the alkyl groups. (1) The metal haloalcoholates are unstable to heat and decompose at 90–220°C. Except for Al(OCH2CF3)3, they are neither distilled nor sublimed even in vacuo. The usual aluminum alcoholates, such as ethoxide and isopropoxide, are easily distilled under reduced pressures. (2) The haloalcoholates are stronger Lewis acids than the usual alcoholates. The acid strength of some aluminum haloalcoholates is even higher than triethylaluminum. The strong acid nature of the aluminum haloalcoholate can be ascribed to the electron-withdrawing effect of halogen. (3) As expected from their strong acid strength, the haloalcoholates induce the cationic polymerizations of vinyl monomers and cyclic ethers, such as styrene, α-methylstyrene, isobutyl vinyl ether, 3,3-bis-(chloromethyl)oxacyclobutane, and tetrahydrofuran. The usual metal alcoholates are weaker acids and do not cause the polymerizations of these monomers. In the ethylene oxide polymerization, both the haloalcoholates and the usual alcoholates showed catalytic activity. However, these two types of alcoholates differ from each other in the catalysis mechanism. For the polymerization of ethylene oxide by the haloalcoholate catalyst, a cationic polymerization mechanism was assumed on the basis of the formation of dioxane as a by-product. The polymerization by the usual alcoholate catalysts is assumed to be of a coordinate anionic mechanism.
Effect of Coexisting Minerals on Graphitization of Carbon. I. Heat Treatments of Carbon under 3 kbar in the Presence of Limestone
Authors: Noda Tokiti , Inagaki Michio , Hirano Shin-ichi , Amanuma Kiyoshi
Published: July 2006

The effect of the presence of limestone on the graphitization of carbon was investigated by the heat treatments of the carbon sample under the quasi-hydrostatic pressure of 3.2 kbar. The carbon sample used was a coke (PV-7) prepared by carbonization of polyvinylchloride up to 680°C. It was placed between two disks of limestone so as to make a sandwich-type specimen. The heat treatments were performed in a simple piston-cylinder type vessel at various temperatures of 800–1300°C for 20–240 min. Above 1000°C, the carbon specimens were obtained as caked tablets. The profiles of (002) diffraction line of these carbon tablets were found to be composite, consisting of a sharp component profile at 26.5° and a broad one at lower angle than 26.2°. The component GM corresponding to the sharp component profile seemed to have the graphite structure. The content of the component GM increased very rapidly with the increase in heat treatment temperatures above 1000°C. Phenomenally, the developement of the graphite structure seemed to be closely related to the recrystallization and the melting of coexisting limestone, but some chemical effects should not be excluded.
Spectrophotometric Study of Metal Chelates of Eriochrom Black T (BT). II. Solution Equilibria between BT and Lead(II)-Nitrilotriacetate (NTA) or Cadmium(II)-N′-(Hydroxyethyl)-ethylenediamine-N, N, N′-triacetate (EDTA-OH)
Authors: Kodama Mutsuo , Sasaki Chifumi
Published: July 2006

The solution equilibria between BT and lead(II)-NTA or cadmium(II)-EDTA-OH chelates were studied spectrophotometrically, and the composition and the stability constants of the BT chelates of these metal ions were determined. In the presence of an excess amount of NTA or EDTA-OH, lead(II) and cadmium(II) ions join with BT to form a chelate with a 1-to-1 composition. The magnitude of the stability constants (1013.19 and 1012.74 respectively, μ=0.30) can explain satisfactorily the well-known experimental fact that BT can be used as a metallochromic indicator in Pb(II)- and Cd(II)-EDTA titrations.
Studies of the Pinacol Rearrangement. IV. The Kinetics and Mechanism of the Rearrangement of meso- and dl-2,2′ Dimethoxybenzopinacol
Authors: Matsumoto Kiyoshi
Published: July 2006

The first-order rate constants of the perchloric acid-catalyzed rearrangements of the meso-and dl-2,2′-dimethoxybenzopinacols were measured in anhydrous acetic acid. A linear correlation of the logarithm of the first-order rate constants (logk) with Hammett acidity function (H0) was obtained in each case. The large positive values of the entropy of activation support the A-l mechanism, which is also supported by the linearities of logk with H0, suggesting that the classical carbonium ion is an intermediate in these processes. The migration aptitude of the meso-isomer decreases with time, while that of dl increases. On the basis of this information, the mechanism of the rearrangement was discussed.
Studies on Cow’s Urine. IV. Determination by Gas-liquid Chromatography of an Acidic Part Obtained from Cow’s Urine
Authors: Suemitsu Rikisaku , Fujita Shin-ichi , Mishima Yasuo , Yoshimura Mitsuo
Published: July 2006

An acidic part obtained from cow’s urine was examined by gas-liquid chromatography. As the major components of the acidic part, benzoic acid, phenylacetic acid, β-phenylpropionic acid, and derivatives in which hydroxyl or methoxyl groups are attached to, respectively, para-, ortho-, and 3,4-positions of the aromatic ring were identified. It is conceivable that these compounds were mainly metabolic products of the phenylalanine, tyrosine, and 3,4-dihydroxy-phenylalanine (DOPA). Moreover, a new metabolic pathway of phenylalanine and its derivatives was tentatively represented.
The Viscosities of Aqueous Solutions Containing Metal Complexes. I. Luteo-type Co(II) and Co(III) Complexes and Ethylenediaminetetraacetato Complexes
Authors: Yasuda Motoo
Published: July 2006

The viscosities of aqueous solutions containing cobalt complexes formed with ammonia, ethylenediamine (en), propylenediamine (pn), 2,2′-bipyridine (bip), 1, 10-phenanthroline (phen), and ethylenediaminetetraacetic acid (H4edta) were determined with a Cannon-Fenske capillary viscometer. Measurements were made in a Shibata viscosity bath maintained at 25±0.01°C. The Jones-Dole viscosity B-coefficients of Co(III) complex cations formed with NH3, en, pn, bip, and phen increase in that order. There is no significant difference between the B-coefficients of [Cobip3]3+ and [Cobip3]2+, or [Cophen3]3+ and [Cophen3]2+. On the other hand, a pronounced difference is found between the B-coefficients of [Coedta]− and [Coedta]2−. This might suggest that there is a marked difference in the structure of [Coedta]− and [Coedta]2− anions.
The Benzylation and Phenylation Reactions of Unsaturated Compounds Using Organo Monohalides and Polynuclear Iron Carbonyl
Authors: Rhee Ilsong , Mizuta Norio , Ryang Membo , Tsutsumi Shigeru
Published: July 2006

The reaction of iodobenzene and benzyl halides (Cl, Br and I) with Fe3(CO)12 (mole ratio; Fe3(CO)12/R–X=1/3) gave the corresponding symmetrical ketones (18–55.2%). The increasing order of the reactivity of the organo halides to Fe3(CO)12 was as follows: iodobenzene<benzyl chloride<benzyl bromide<benzyl iodide. In the reaction of benzyl chloride with Fe3(CO)12, when two-thirds of the Fe3(CO)12 had been used, or moles equal to benzyl chloride, the yields of the ketones were increased to 87% (total yield). The same reaction in the presence of olefin produced benzylation or phenylation products of the olefin; for example, the reaction of benzyl iodide with Fe3(CO)12 in the presence of acrylonitrile (in tetrahydrofuran) gave 4-phenylbutyronitrile (30.2%) and 4-cyano-6-phenylhexanonitrile (10.0%). When olefin with a higher coordinating ability to iron carbonyl was used, the yields of the benzylated adducts of the olefin decreased, while when the more reactive organo halide was used, the yields increassed. Thus, it was postulated that organo halide reacted with Fe3(CO)12 to form the σ-complex, benzyl(or phenyl)iron carbonyl halide, as an intermediate to the benzylation (or phenylation) products. The benzylation and phenylation reactions proceeded smoothly in a polar solvent (dimethylformamide or ethanol) to give high yields. The benzylation of phenylacetylene did not occur in benzene, but in a polar solvent it proceeded, giving 1,3-diphenylpropane and -propene. The mechanistic aspects of these reactions are discussed below.
Mechanism of Asymmetric Reactions. II. Kinetical Resolution of Racemic Primary Amines by Means of Sulfonylation with (+)-Camphor-10-sulfonyl Chloride—Preferential Conservation of an Absolute Configuration in the Asymmetric Sulfonylation of Racemic Amines
Authors: Okamoto Kunio , Minami Etsuo , Shingu Haruo
Published: July 2006

α-Phenylethylamine (I), α,β-diphenylethylamine (II), α-(β-naphthyl)-ethylamine (III) α-(α-naphthyl)-benzylamine (IV), α-pipecoline (V), 2-aminobicyclo[2.2.2]octane (VI), and methylamine (VII) have been partially sulfonylated by (+)-camphor-10-sulfonyl chloride in benzene (or toluene); the optical rotations for the unsulfonylated amines, partially resolved, have been measured. Examination of absolute configurations for the amines indicates that the (R) enantiomers of these amines (I, II, V and VII, including neomenthylamine (VIII) and isomenthylamine (IX)) react faster than the respective (S) enantiomers, with exception of III. The rate for the sulfonylation of (−)-menthylamine with (+)-camphor-10-sulfonyl chloride have been determined in toluene at the temperatures ranging from −20 to −40°C; the rate ratio of the (+)-menthylamine to the (−)-amine has been estimated from the extent of the kinetical resolution of the (±)-menthylamine. Kinetical implication of the coincidence of the preferred absolute configurations has been discussed.