bluuebunny/crossref_metadata_2025_split huggingface dataset:
Preparation of Esters of Phosphoric Acid by the Reaction of Trivalent Phosphorus Compounds with Diethyl Azodicarboxylate in the Presence of Alcohols
Authors: Mitsunobu Oyo , Yamada Masaaki , Mukaiyama Teruaki 
Published: July 2006

Abstract
Trivalent phosphorus compounds, phosphine or trialkylphosphites, have been oxidized by means of diethyl azodicarboxylate and either benzyl or allyl alcohol to give the corresponding phosphine oxide or trialkyl phosphates. The reaction was then extended to the phosphorylation of alcohols. When allyl diethyl phosphite was treated with diethyl azodicarboxylate in the presence of an alcohol at room temperature, a corresponding alkyl diethyl phosphate and diethyl N-allyl hydrazodicarboxylate were obtained in good yields. On the other hand, when phenol was treated with allyl diethyl phosphite and diethyl azodicarboxylate, diethyl phenyl phosphate, allyl phenyl ether and diethyl hydrazodicarboxylate were obtained. The mechanism of their formation will also be discussed.
Electron Spin Resonance Spectra of X-Irradiated Single Crystals of 3, 3′-Dithiodipropionic Acid: “B cos2θ” Rule for Sulfur Radicals
Authors: Kurita Yukio 
Published: July 2006

Abstract
The ESR of X-irradiated single crystals of 3, 3′-dithiodipropionic acid was measured at room temperature. From the analysis of the anisotropy in the spectra, the free radical produced was confirmed to be of the HO2OC·H2CH2·S form. The principal values of the g factor are 2.003, 2.025, and 2.055, while the isotropic coupling constants for the two β protons are 12.4 G and 5.3 G. In this free radical the unpaired electron is mainly concentrated in a 3pπ orbital of the sulfur atom. For the isotropic coupling constant of the β proton in this type of radical, the “Bcos2θ” rule is applied successfully using the value of 12.8 G for B.
Reaction of Aliphatic Ketones with α-Cyano-α, β-unsaturated Acid Derivatives
Authors: Sato Kikumasa , Kurihara Yoshie , Inoue Seiichi 
Published: July 2006

Abstract
The reaction of several aliphatic ketones with α-cyano-α, β-unsaturated acid derivatives has been studied. Ethylidenecyanoacetic acid reacted with a large excess of acetone in an autoclave at 150–160°C to give 3-methyl-5-oxohexanonitrile, which was considered to be produced by the decarboxylation of the Michael-type adduct of acetone onto the acid. Similar adducts were obtained by the reaction of the acid with methyl ethyl ketone, cyclohexanone, and ethyl laevulinate. The reaction of ketones with ethyl ethylidenecyanoacetate did not afford Knövenagel-type condensates, but Michael-type adducts in appreciable yields, for example, ethyl 2-cyano-3,4-dimethyl-5-oxohexanoate from methyl ethyl ketone. Diethyl ethylidenemalonate also gave Michael-type adducts. These results seem to suggest that the γ-methyl group of ethylidenecyanoacetic acid or its ester is not active enough to give Knövenagel-type condensates with aliphatic ketones, and that, therefore, the Knövenagel-type reaction is preceded by the Michael-type addition reaction of ketones onto the activated carbon-carbon double bond.
Photo-induced Reactions. V. The Photochemical Reaction of a 2-Cyclohexenone, Pummerer’s Ketone
Authors: Matsuura Teruo , Ogura Katsuyuki 
Published: July 2006

Abstract
The ultraviolet irradiation of Pummerer’s ketone (VIII) in methanol yielded a 1:1 methanol adduct IX in a good yield; this is a new type of product in the photochemical reaction of a 2-cyclohexenone, i.e., a photochemical Michael-type addition of an alcohol to form a 3-alkoxy-cyclohexanone. The irradiation of VIII in isopropyl alcohol yielded an adduct, XI, analogous to IX and a photoketone, XIII, isomeric to VIII. The photoketone was also obtained by the irradiation of VIII in t-butyl alcohol, dioxane, or benzene. The mechanisms of these reactions are discussed.
Aminocyclitols. XVII. A Facile Synthesis of 2-Deoxystreptamine
Authors: Suami Tetsuo , Lichtenthaler Frieder W , Ogawa Seiichiro , Nakashima Yasuo , Sano Hiroshi 
Published: July 2006

Abstract
Bromination of myo-inosadiamine-l,3 dihydrochloride or its di-N-acetyl derivative with acetyl bromide and acetic anhydride yielded pentaacetyl-2-bromo-2-deoxy-scyllo-inosadiamine-1,3 (III), which upon reductive debromination afforded pentaacetyl-2-deoxystreptamine (IV). The configurations of the new compounds obtained were established by nuclear magnetic resonance and chemical evidences. A mechanism of the bromination reaction is presented, based on the configuration of the bromo-compound.
The Electron Spin Resonance of Mn2+ Ion in Polyphosphate
Authors: Miura Masaji , Hasegawa Akinori , Watanabe Masayuki 
Published: July 2006

Abstract
A part of cation in polyphosphate was replaced with Mn2+ ion. Zero-field splitting parameter D due to the crystal field with axial symmetry was estimated according to Allen’s method from the ESR spectrum of Mn2+ ion. The value of D changes with the change in the state of polyphosphate, crystalline or glassy. As the degree of polymerization of sodium polyphosphate glass decreases, the value of D increases and approaches to the value corresponding to the crystalline state. These phenomena were interpreted as due to the disorderness of glassy state. The value of D was found to change with the variation of the kind of cation in polyphosphate. This was explained in terms of the effective cationic field.
Dissociation Pressures of Various Metallic Oxides
Authors: Kodera Kumasaburo , Kusunoki Isao , Shimizu Shinkichi 
Published: July 2006

Abstract
Gases evolved during a vacuum heat treatment of various oxides were analyzed by means of an omegatron mass spectrometer. Carbon dioxide, carbon monoxide and water were detected as main gases evolved at lower temperatures. Oxygen due to thermal dissociation of ZnO, CdO, NiO, CuO, Cu2O, and WO3 was found at high temperatures. In the case of MoO3, however, evolution of oxygen was not observed. The equilibrium pressures of the evolved gases over these oxides have been measured with a McLeod gauge and a Knudsen gauge. The oxygen dissociation pressures of ZnO, CdO, NiO, CuO, and Cu2O were measured and compared with the calculated values.
The Non-Newtonian Viscosity of Dilute Aqueous Solution of Methylcellulose
Authors: Iso Naomichi , Yamamoto Daijiro 
Published: July 2006

Abstract
The viscometric behavior of a dilute aqueous solution of methylcellulose was studied by tilting capillary viscometers. The intrinsic viscosity was obtained by the extrapolation of Martin’s plots on the assumption that the plots were linear down to an infinite dilution. The intrinsic viscosity obtained increased with the rate of shear over the range of 200–1200 sec−1. Huggins’ constant, k′, the temperature coefficient of the intrinsic viscosity, d[η]/dT, and the energy of the activation of flow, Ev, decreased with the rate of shear. From the data of d[η]/dT and Ev thus obtained, it has seemed reasonable to assume that the methylcellulose chain has a relatively small flexibility and a strong tendency toward alignment with a flowing stream. This may be the main reason why the viscosity of the dilute aqueous solution of methylcellulose is non-Newtonian.
A Study of Charge-Transfer Complexes. VII. Interactions between the Alkyl- or Arylsubstituted Pyrroles and Chloranil or Tetracyanoethylene
Authors: Matsuo Taku , Shosenji Hideto 
Published: July 2006

Abstract
The charge-transfer (CT) bands of complexes of alkylsubstituted pyrroles and chloranil or tetracyanoethylene (TCNE) were found to consist of two closely situated peaks. The peaks were assigned to transitions originated from the highest occupied, and second-highest occupied orbitals of the donor. The energy of the CT absorption band is hardly affected even by the presence of a bulky substituent such as a t-butyl group at the pyrrole nitrogen. Hence, the acceptor molecules were thought not to be close to the 1-position of the pyrryl group. In the case of 1-phenylpyrrole, the first CT bands are at almost the same positions as those of the corresponding complexes of 1-methylpyrrole. The bands show red shifts if methyl groups are introduced either on the pyrryl group or on the phenyl group, so that the planes of the two groups are twisted around the N–C bond between them. Thus the acceptor molecules were concluded to interact mainly with the pyrryl group.
Microwave Spectrum of o-Difluorobenzene
Authors: Hatta Aritada , Hirose Chiaki , Kozima Kunio 
Published: July 2006

Abstract
The microwave spectrum of o-difluorobenzene has been studied in the 7.8- to 28-Gc/sec region, R- and Q-branch transitions of the a-type being assigned for the lowest vibrational state. The rotational constants obtained are A=3263.55 Mc/sec, B=2227.91 Mc/sec, and C=1323.87 Mc/sec. Four possible sets of structural parameters were obtained. seems probable that the angle made by two C–F bonds is larger than 60°. The value of the dipole moment obtained is 2.46±0.03 D.
Radicals Produced by UV Irradiation of Acridan and Acridine in Glassy and Crystalline Medium at 77°K
Authors: Niizuma Shigeya , Koizumi Masao 
Published: July 2006

Abstract
Choosing two groups of solvent a) methanol, ethanol, isopropanol (glassy at liquid nitrogen temperature) and b) t-butanol, benzene, tetrahydrofuran (crystalline at liquid nitrogen temperature), ESR studies have been made on the irradiated solutions of A] acridine (A)+acridan (AH2) (1:1), B] A alone, and C] AH2 alone at 77°K. 1) 365 mμ irradiation of A] and B] in the solvents of a) group does not cause any photochemical reaction, whereas in the solvents of b) group, the A*+AH2→2AH· reaction occurs. A resultant singlet ESR line has been assigned to AH·. 2) Irradiation of A] and C] with the entire output from a superhigh pressure mercury lamp gives, for solvents of group a), the ESR spectra which can be attributed mainly to alcohol radicals (RCHOH) but gives electronic absorption spectra ascribed only to AH· ; for the solvents of group b) the results were almost the same as in 1).
The Crystal and Molecular Structure of an Isomer of Bis-(1,2-diethoxycarbonyl-ethyl)tin Dibromide
Authors: Yoshida Mamoru , Ueki Tatzuo , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao , Omae Iwao , Kikkawa Shoichi , Matsuda Sumio 
Published: July 2006

Abstract
Low mp isomer of bis-(1,2-diethoxycarbonyl-ethyl)tin dibromide (mp 114–115°C) crystallizes in a monoclinic form: a=11.85, b=20.24, c=9.79 Å, β=101.3°; space group, P21/a; and four molecules are contained in a unit cell. Crystal structure was established by the heavy atom method. The coordination about the tin atom is nearly octahedral. Two bromine atoms attached to the tin atom are in cis-positions. Two ligands, 1,2-diethoxycarbonyl-ethyl groups, are both bound to the tin atom by carbon and oxygen, forming five-membered rings. These rings are rather puckered, and one is in d-form and another in l-form.
The Chemistry of Protactinium. VI. A Study of the Sulfato-Complex of Pa(IV) by Means of TTA-Benzene Extraction
Authors: Mitsuji Toshikazu 
Published: July 2006

Abstract
The behavior of Pa (IV) during extraction with TTA was investigated in perchlorate, chloride, and sulfate solutions (pH 0.4–1.1). In perchlorate and chloride solutions, the extraction equilibrium may be written as:
Pa(OH)_2^2++4HT\ightleftharpoonsPaT_4+2H_2O+2H^+
On the other hand, the extraction by TTA from the sulfate solution may be described as:
Pa(SO_4)(OH)^++4HT\ightleftharpoonsPaT_4+HSO_4^-+H_2O+2H^+
Therefore, the formation of the sulfato-complex of Pa(IV) is considered to occur as follows:
Pa(OH)_2^2++HSO_4^-\ightleftharpoonsPa(SO_4)(OH)^++H_2O
The equilibrium constant for the above reaction has been determined to be 320 at the ionic strength of 0.50 (temperature: 10±0.5°C).
The Reaction of the Ester with Acyl Chloride in the Presence of Aluminum Chloride. VIII. The Attempted Synthesis of the Carbethoxy Derivative of Polymalonylphenylene
Authors: Matsui Kiyotada , Motoi Masatoshi , Nojiri Tetsuro , Wakabayashi Kohtsuchi 
Published: July 2006

Abstract
The treatment of ethyl acetoacetate with terephthaloyl chloride in the presence of two equivalents of aluminum chloride in nitrobenzene at 55°C affords a polymer which may be designated as an aluminum chelate of the polymalonylphenylene derivative with some carbethoxy groups.
A Kinetic Study of the Metal Ion-catalyzed Glycolysis of Benzonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Noguchi Yoshitaka 
Published: July 2006

Abstract
The kinetics of the lead ion-catalyzed glycolysis of benzonitrile were studied in the presence of water. The experimental results indicated that the rate of the formation of ammonia followed the first-order rate law with respect to the concentrations of benzonitrile and of water. For the concentration of the catalyst, the rate found was of a 0.44 order. It was observed that the product, β-hydroxyethyl benzoate, exhibited an inhibiting effect on the glycolysis. The effects of substituents on benzonitrile were found to fit the Hammett rule. The reaction was remarkably influenced by the type of glycol used. The reaction also proceeded through the hydrolysis of benzonitrile, followed by the glycolysis of the benzamide thus formed. The rate of the glycolysis of benzamide was about one-third that of benzonitrile, which is the main reaction in the system. The reaction of imidate formation possessed a small equilibrium constant at a high temperature, but it had a high reaction rate. The proposed mechanism for these glycolysis reactions is as follows: the addition of glycol to benzonitrile yields imidate, which then forms a chelate compound with a metal ion. The imidate activated by the formation of the chelate is easily hydrolyzed by water to form ester and ammonia. This ester tends to chelate to the metal ion and so inhibits the reaction.
The Kinetics of the Metal Ion-catalyzed Glycolysis of Terephthalonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Ishioka Ryoji 
Published: July 2006

Abstract
The kinetics of the lead ion-catalyzed glycolysis of terephthalonitrile have been studied in the absence of and in the presence of water. In the absence of water, scarcely any formation of β-hydroxyethyl p-cyanobenzoate is observed, but some orthoesters are formed. The reaction rate data obtained in the absence of water are found to fit a reversible consecutive reaction scheme in which some basic compounds are involved as the intermediates. In proportion to the increase in the concentration of water, such intermediates as the orthoesters and basic compounds are hydrolyzed more rapidly to form β-hydroxyethyl p-cyanobenzoate, but simultaneously the hydrolysis of terephthalonitrile and the basic intermediates also takes place in the reaction mixture, thus yielding amide.
Stereochemical Studies of Monoterpene Compounds. V. The Rotational Conformation of the Acetyl Group of 10-Nor-8-oxomenthols and 10-Nor-8-oxocarvomenthols
Authors: Suga Takayuki , Shishibori Tsuyoshi , Matsuura Tamon 
Published: July 2006

Abstract
The preferred rotational conformation of the acetyl group of (+)-10-nor-8-oxoneomenthol (I), (−)-10-nor-8-oxomenthol (II), (−)-10-nor-8-oxocarvomenthol (III), and (+)-10-nor-8-oxoneocarvomenthol (IV) has been examined by a combination of conformational analysis by a priori calculation and variable-temperature circular dichroism and infrared spectrum measurements. Compound I exhibited an inversion in the sign of the Cotton effect upon a change in the solvent. This phenomenon was interpreted as indicating the conformational change Ia\ightleftarrowsIb. The cause of the change was ascribed to the formation and subsequent rupture of the intramolecular hydrogen bond. Compound II exhibited a solvent-depending circular dichroism curve similar to the curve of I; this was explained as indicating the existence of a conformational equilibrium between the free conformer, IIa, and the internally-hydrogen-bonded conformers, IIb, IIc, and IId. Furthermore, compounds III and IV were found to take preferentially the IIIa–IIIb and IVa–IVb conformations respectively.
Acid-Catalyzed Isomerization of 1,3,4,5-Tetra-O-acetyl-2-deoxy-l-sorbopyranos-2,3-ene
Authors: Katsuhara Mitsuru , Wakahara Shigeru , Tokuyama Kanji 
Published: July 2006

Abstract
An acid-catalyzed reaction in acetic anhydride was found to isomerize 1,3,4,5-tetra-O-acetyl-2-deoxyl-l-sorbopyranos-2,3-ene (V) to four new unsaturated compounds. When the reaction was allowed to continue for a longer period, they underwent polymerization, but did not afford 2-hydro-xyacetylfuran acetate (XXVIb). The reaction in acetic acid containing water was shown to mainly convert V into XXVIb. This reaction pathway was thought to be different from the above.
Synthetic Studies of α-Tocopherol. II. Synthesis of Trimethyl-benzoquinone
Authors: Ichikawa Takehiko , Owatari Hiroko , Kato Tetsuya 
Published: July 2006

Abstract
Trimethylbenzoquinone (XII), a raw material for the synthesis of trimethylhydroquinone (XIII), was synthesized from trimethylcyclohexenones and trimethylcyclohexene by oxidation. Ethyl α-propionylpropionate (II) prepared from ethyl propionate was condensed with methyl vinyl ketone to yield 4-methyl-4-ethoxycarbonylocta-3,7-dione (IV), which was then dehydrated with beryllium chloride to give 2,3,6-trimethyl-6-ethoxycarbonyl-2-cyclohexen-1-one (V). The product (V) was heated with alkali to give 2,3,6-trimethyl-2-cyclohexen-1-one (VI). The refluxing of a solution of IV in a mixture of acetic acid and hydrochloric acid also gave rise to VI. When II was condensed with crotonaldehyde, 2,5,6-trimethyl-2-cyclohexen-1-one (VIII) was obtained in a single step. 1,4(or 1,5)-Dimethyl-5-(or 4)-formyl-1-cyclohexene (IX), obtained by the Diels-Alder reaction of crotonaldehyde with isoprene, was reduced by hydrazine hydrate to give 1,4,5-trimethyl-1-cyclohexene (X). X was oxidized with t-butyl chromate and acetic anhydride to give 3,5,6-trimethyl-2-cyclohexen-1-one (XI). VI, VIII, XI, and X were oxidized with t-butyl chromate and acetic anhydride to give XII in 53, 52, 22, and 12% yields respectively. The oxidation of VIII by selenium dioxide gave XII in a 23% yield, but only a trace of XII was formed by the similar oxidation of X.
Synthesis of 4,5-Di- and 1,4,5-Trisubstituted Imidazole Derivatives from 4,5-Dicyanoimidazole
Authors: Yamada Yoshitaka , Kumashiro Izumi , Takenishi Tadao 
Published: July 2006

Abstract
The chemical reactivities and the synthesis of various derivatives of 4,5-dicyanoimidazole formed by heating a solution of hydrogen cyanide in liquid ammonia were studied, as were the partial hydrolysis, hydrogenation, and addition reaction of cyano groups and the alkylation, cyano-ethylation, and vinylation of the imidazole ring. From these experiments, a few new compounds were synthesized, which had been expected as intermediates of polymers containing imidazole rings.
Measurement of Adsorbed Amount of Sodium Dodecylsulfate at Gas-Solution Interface by Radiotracer Method Using Tritium-Labeled Compounds
Authors: Muramatsu Mitsuo , Tajima Kazuo , Sasaki Tsunetaka 
Published: July 2006

Abstract
Sodium dodecyl-2,3-3H,3Hsulfate (SDS) was synthesized from non-radioactive dodecanol, and the adsorbed amount of SDS at the gas-water interface, Γ, was directly measured by the radiotracer method with the use of 2π gas-flow windowless counter and humidified propane as a flow-gas. Because of a very soft nature of tritium β-rays, surface radioactivity is exclusively due to the solute adsorption compared with the large contribution from the bulk of the solution as in the case of 14C or 35S labeled detergents. Therefore the use of 3H labeled compounds enables the determination of the amount of adsorption in high accuracy, even in the region of high concentration beyond the critical micelle concentration (CMC) of SDS solution. However, no reliable reports have appeared as yet on the studies of adsorption of surfactant at gas-solution interface using 3H labeled compounds. Our measurement was carried out under exactly specified conditions, namely using chemically and radiochemically pure sample and under the condition free from evaporation. It was confirmed that Γ increased with the increase of SDS concentration and approached the saturation value of 5.9×10−10 mol/cm2 or 28.2 Å2/molecule at the concentration higher than 6×10−3 mol/1000 g solution and beyond CMC. Furthermore, Γ proved to be independent of the acidity of solution above pH 4, while it increased with increasing acidity below pH 4. The phenomenon is explained by the presence of hydrolytically formed dodecylsulfuric acid whose surface activity is higher than that of SDS.
Radiolysis of CoIII-EDTA in Aqueous Solution; The Effect of pH
Authors: Matsuura Niro , Shinohara Nobuyoshi , Nishikawa Masaru , Takizawa Masao 
Published: July 2006

Abstract
The hydrogen and hydrogen peroxide produced in the radiolysis of CoIII-EDTA (CoIIIY−) in various pH’s have been measured. G∞(H2) in the deaerated system sharply dropped from the value of 3.2 at pH&lt;1 to the value of 0.8 at pH&gt;4 where G∞ denotes a limiting value which is reached with increasing solute concentration. G∞(H2O2) in the aerated system was found to be 2.5–2.0. G∞(–CoIIIY−) (=4.4) was not affected by the addition of N2O. G∞(N2) and G∞(H2) were found to be 2.6 and 0.8 respectively. From the results, it is concluded that H atoms and OH radicals reduce Co(III) to Co(II) through the dehydrogenation from the ligand, while eaq− reduce the complex without any degradation of the ligand.
The Electronic and Vibrational Spectra of Oxalyl Bromide
Authors: Shimada Hiroko , Shimada Ryoichi , Kanda Yoshiya 
Published: July 2006

Abstract
The infrared and Raman spectra of oxalyl bromide have been observed. The spectral features suggest that this molecule is planar and trans at room temperature. An assignment has been given for all the fundamental vibrational frequencies. The ultraviolet absorption spectrum of oxalyl bromide has been studied in cyclohexane and in the vapor. The spectrum consists of four absorption systems. These were ascribed to a 3Au(n, π*)←1Ag, a 1Au(n, π*)←1Ag, the second 1Au(n, π*)←1Ag and a 1Bu(π, π*)←1Ag transitions, respectively. Vibrational analyses have been made for the 3Au(n, π*)←1Ag and the first 1Au(n, π*)←1Ag systems.
An X-Ray Determination of the Structure of Motiol Iodoacetate
Authors: Nishi Yoriko , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao 
Published: July 2006

Abstract
The molecular configuration of motiol has been determined by the X-ray crystal analysis. The crystal of motiol iodoacetate, C32H52O2I, is monoclinic with two molecules in a unit cell of dimensions; a=17.37, b=6.78, c=13.04 Å and β=99.6°, the space group being P21. The crystal structure was solved by the heavy atom method. The atomic coordinates and anisotropic temperature factors were refined by block-diagonal matrix least-squares method. The structure determined is, in general, compatible with that derived chemically. The rings A and D are of a chair form, and the rings B and C are of a semi-chair. The molecule bends at the rings B and C to make a bow as a whole. All but one of the methyl groups are in axial junction.
Anticatalytic Effect of Mn(II) in the Silver Catalyzed Oxidations by Peroxydisulphate
Authors: Sengar H G S , Gupta Y K 
Published: July 2006

Abstract
Mn(II) has been found to be an anticatalyst in the silver catalyzed oxidations of oxalate, citrate, tartrate, malonate and arsenious acid and the limiting value of the rate constants in each case is about 0.4 l/mol-min at 35°C which is very much comparable to the rate constant for the separate silver catalyzed oxidation of Mn(II), H2O, Ce(III), N2H4 and vanadyl ion. A mechanism has been proposed in which the simultaneous oxidation of Mn(II) and the organic substrate or arsenious acid takes place and when sufficiently large concentration of Mn(II) is present, the latter oxidation is almost completely suppressed. The oxidations of citrate and tartrate are consecutive reactions. The first faster reaction is followed by the second slower reaction.