bluuebunny/crossref_metadata_2025_split huggingface dataset:
Azirines. I. The Reaction of 2-Phenylazirine with Carbanions
Authors: Sato Shimao , Kato Hiroshi , Ohta Masaki 
Published: July 2006

Abstract
An attempt to prepare 2-phenylazirine by treating acetophenone dimethylhydrazone methiodide with methylsulfinyl carbanion gave 2, 4-diphenylpyrrole instead of 2-phenylazirine. The reaction of 2-phenylazirine with the carbanions derived from acetophenone, ethyl benzoylacetate, and benzyl cyanide gave the corresponding pyrrole derivatives by ring enlargement.
Syntheses of Phenyl Formates and Naphthyl Formates with Acetic Formic Anhydride
Authors: S\={o}fuku Sh\={o}suke , Muramatsu Ichiro , Hagitani Akira 
Published: July 2006

Abstract
A new method for the syntheses of phenyl and naphthyl formates has been devised. The formates were obtained in good yields from phenols and naphthols with acetic formic anhydride, which had been prepared from formic acid and ketene. The formyl ester of N-hydroxysuccinimide was also prepared by the same method.
Stereoregularity of Poly-(R)-2-ethylaziridine
Authors: Tsuboyama Kaoru , Tsuboyama Sei , Yanagita Masaya 
Published: July 2006

Abstract
Poly-(R)-2-ethylaziridine (I) was obtained by three different procedures: (A) the polymerization of (R)-2-ethylaziridine (II) by boron trifluoride-etherate, (B) the polymerization of the aziridine in the presence of ammonium chloride in liquid ammonia, and (C) the reaction of (R)-2-amino-l-bromobutane hydrobromide (III) with caustic alkali. The stereoregularity of the polymer I may be assumed to be fairly high as a result of comparing the specific rotations of the above polymers. In order to evaluate this assumption, the addition reaction of the aziridine and diethylamine was carried out as a model experiment under experimental conditions similar to those of the polymerization (A). On the basis of the data as analyzed by gas chromatography, it is concluded that the ring opening at the primary carbon takes place over 99.4%. This implies that the ring cleavage at the primary carbon in the polymerization occurs over 180 units successively. Considering the molecular weight of the polymer I (3500–5000, 50–70 monomer units), one can assume that the configuration of the polymers obtained here perfectly retains that of the monomer and that the polymer is “isotactic.”
Studies of Organic Peroxides. VIII. The Reaction of Benzoyl Peroxide with 5, 5′-Indigo-disulfonic Acid
Authors: Kashino Setsuo , Nishimura Norio , Ino Kohei , Hasegawa Shigeo 
Published: July 2006

Abstract
The reaction of benzoyl peroxide with 5, 5′-indigo-disulfonic acid was studied in ethanol. The effect of the p,p′-substituents of benzoyl peroxide on the reaction rate was investigated. It was found that the reaction is a bimolecular process. Either electron-attracting substituents or electron-releasing substituents promote the reaction. This was interpreted by means of the multicenter mechanism. The electron absorption spectra of the reaction mixture showed the formation of a reasonably stable complex in ethanol. This complex is decomposed by water to 5-isatinsulfonic acid and 5, 5′-indigo-disulfonic acid.
The Chemiluminescence of Indole Derivatives. I
Authors: Sugiyama Noboru , Akutagawa Masamoto , Gasha Taketoshi , Saiga Yo , Yamamoto Hiroshi 
Published: July 2006

Abstract
The chemiluminescence of forty-one indole derivatives has been investigated by using two types of reaction mixtures: (A) the EtOH-KOH-H2O2-K3Fe(CN)6-Sample and (B) the DMSO-KOH-Sample. In both systems the reactions were carried out in the presence of air. The light intensity of chemiluminescence was measured by the deflection of the microammeter of the photometer or recorded by a connected automatic recorder. The relative light intensity (RLI), the ratio of the maximum intensity of the chemiluminescence of the sample to that of indole, was also measured. The electron-repelling group, such as hydroxyl and substituted aminovinyl group, at the 3- or 5-position enhanced the RLI, but alkyl, acetyl, formyl groups or chlorine at the various positions had little effect or a negative effect on the RLI. Some of the compounds showed a maximum intensity soon after the reagents were mixed, while some others slowly showed a maximum, which then decayed slowly.
Cyclic Acetylenes. X. A Transannular Hypochromism Observed in a Cyclic Diacetylene Containing a Naphthalene Nucleus
Authors: Ando Takashi , Nakagawa Masazumi 
Published: July 2006

Abstract
A cyclic diacetylene (XIa) has been synthesized by the oxidative coupling of 1, 5-bis(propargyloxymethyl)naphthalene (X) with a cyclic dimer (XIb) and a cyclic trimer (XIc). The electronic spectra of XIb and XIc have been found to be almost identical with that of naphthalene with respect to the location of the absorption maxima and the intensities. On the other hand, a marked decrease in the absorption intensities has been observed in the spectrum of the cyclic monomer (XIa). An inspection of the Dreiding model of XIa indicates that the two conformations (A and B) can retain the maximum distance between the dyine unit and the naphthalene nucleus. On the basis of the molecular model, the distance between the two chromophores and the angle between the short axis of the nucleus and the bridging chain have been estimated to be 2.26 Å, 21° for A and 2.12 Åand 38° for B. Employing these data, the hypochromic effect exerted by the diyne chromophore on the absorption of the naphthalene nucleus has been calculated according to the theory of Tinoco and Rhodes, resulting in a fairly good agreement with the observed values. Inversely, the calculation of the distance and the angle between the two chromophoric groups using the observed hypochromic effect has also given reasonable values. Therefore, the hypochromism observed in the cyclic diacetylene (XIa) has been attributed to the operation of dispersion-force interaction between diyne unit and the naphthalene chromophore.
Asymmetric Synthesis in the Methoxy-mercuration of α, β-Unsaturated Esters
Authors: Oda Junichi , Nakagawa Tsutomu , Inouye Yuzo 
Published: July 2006

Abstract
The methoxy-mercuration of (−)-menthyl crotonate, cinnamate, and β-methylcinnamate resulted in partial asymmetric syntheses of the corresponding β-methoxylated derivatives, (−)-R-β-methoxybutyric acid, (−)-S-β-methoxy-β-phenylpropyl alcohol, and (−)-S-β-methoxy-β-phenylbutyl alcohol. The results suggested an ionic mechanism involving a cyclic mercurinium ion as an intermediate, formed by the electrophilic attack of mercuric acetate from the least-hindered side of the double bond in the Cram-Prelog model of the systems, followed by the attack of the methoxy anion from the opposite side. The reaction mechanism leading to the predominant enantiomers was discussed.
The Surface Activity of Tetrabutylammonium Halides in the Aqueous Solutions
Authors: Tamaki Kunio 
Published: July 2006

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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&lt;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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.