bluuebunny/crossref_metadata_2025 huggingface dataset:
The Reaction of Alcohols with Hexamethylphosphoric Triamide
Authors: Arimatsu Seiji , Yamaguchi Ryohei , Kawanisi Mituyosi
Published: July 2006

The thermal treatment of 4-homoadamantanol and bicyclo[3.3.1]nonanols with hexamethylphosphoric triamide (HMPT) gave the corresponding olefins in moderate yields. The application of this dehydration method to a system in which olefin formation was regarded as difficult or impossible stereochemically led to various types of reactions, i.e., reduction, substitution, and phosphorodiamidation. Upon being heated in HMPT, 2-adamantanol afforded 2-adamantyl tetramethylphosphorodiamidate, whereas 1-adamantanol was transformed into adamantane via 1-adamantyl tetramethylphosphorodiamidate. In the case of allylic or benzylic alcohols, dimethylamino-substituted compounds were obtained. The reduction of the amount of HMPT promoted the formation of an ether, while dibenzhydryl ether was produced exclusively from benzhydrol. The mechanism of these reaction is discussed.
Chemiluminescence of Succinylfluorescein and Related Compounds. I. Emitting Species Produced by the Reaction of Succinylfluorescein with Oxygen in Aprotic Solvents
Authors: Kamiya Isao , Aoki Keizo
Published: July 2006

In the course of our studies of the chemiluminescence of xanthene dyes, we found the violet chemiluminescence emission (CL-emission) resulting from the reaction of succinylfluorescein with oxygen in an aerated alkaline aqueous system of a high concentration of an aprotic solvent (DMSO or DMF), an especially intense emission occurring in aerated dry DMSO or DMF with tert-BuOK as base. The CL-emission comprised two emission components: an intense violet emission (a peak, at 410 nm) whose spectral distribution was similar to that of the fluorescence band which appeared during the course of the reaction, and a weak greenish-yellow emission similar to the fluorescence of the dye. By isolating and identifying the violet-fluorescent reaction product with an authentic sample, and by comparing the CL-emission with the fluorescence emission of the isolated product, it was concluded that the violet CL-emission may be attributed to the formation of an excited dianion of 3,6-dihydroxyxanthone. The reaction path leading to the dioxetane intermediate which will be produced by the elimination of a proton from the C atom at the β-position of the dye, followed by the oxygenation via the caged radical pair, was discussed as a likely mechanism for the formation of the excited dianion.
Proton Magnetic Resonance in Organic Free Radicals, BDPA–Bz and p-Cl-BDPA
Authors: Uchino Kazuhiro , Yamauchi Jun , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo
Published: July 2006

The proton NMR absorption spectra from 1.3 to 77 K in two organic free radicals, BDPA–Bz and p-Cl-BDPA, have been measured on powder samples which undergo a magnetic phase transition from a paramagnetic to an antiferromagnetic state at the temperatures of 1.695 and 3.25 K respectively. The behavior of the NMR absorption spectra associated with the magnetic phase transition has been studied for the first time in the organic free radicals and interpreted in terms of the hyperfine interaction. These results are then compared with those of the TANOL radical, which is a linear antiferromagnet with no magnetic phase transition down to 1.3 K.
Asymmetric Reactions. IX. On the Catalytic Hydrogenation of Olefinic Compounds with Bis(dimethylglyoximato)cobalt(II)-base Complex
Authors: Takeughi Seiji , Ohgo Yoshiaki , Yoshimura Juji
Published: July 2006

Examination of the catalytic hydrogenation of twenty-one olefinic compounds with bis(dimethylglyoximato)cobalt(II)-pyridine complex indicates that all (Remark: Graphics omitted.) type olefinic compounds having an electron-withdrawing and a weakly electron-donating substituent are reducible. Isolation and further hydrogenation of the alkyl complexes in the case of (Remark: Graphics omitted.) type olefinic compounds, and deuterogenation of α-phenylacrylophenone support the view that α-alkyl complexes are the intermediates in hydrogenation. It is concluded that the electron-withdrawing effect accelerates both the first (alkyl complex formation) and the second (reductive-cleavage of alkyl moiety) steps, while steric compression prevents the first step and accelerates the second step. The reaction mechanism is discussed.
The Relation between the Electronic Spectra and the Oxidation and Reduction Potentials of Benzenoid Hydrocarbons
Authors: Kubota Tanekazu , Miyazaki Hiroshi , Ezumi Kiyoshi , Yamakawa Masumi
Published: July 2006

It was shown that the 1La band of benzenoid hydrocarbons is in a linear relation to (E1⁄2red–E1⁄2oxd) value led from the half-wave reduction and oxidation potentials. The theoretical background and the binding conditions of the application of this relation were clearly given.
The ESR Spectra of Bis(t-butyl and ethyl acetoacetato)copper(II) Complexes in Various Hydrocarbon Solvents
Authors: Yokoi Hiroshi
Published: July 2006

The X-band ESR spectra of bis(t-butyl acetoacetato)copper(II) and bis(ethyl acetoacetato)copper(II) in several non-coordinating solvents of hydrocarbon were measured at 77 K. Remarkable solvent effects on dimer formation were revealed for the complexes.
The Thermal Behavior of Silanol Groups of Silica Gel as Studied by Infrared Spectroscopy. I
Authors: Kondo Seiichi , Muroya Masa-aki , Fujii Kenzo
Published: July 2006

The thermal behavior of the silanol of silica gel has been studied by quantitative infrared spectroscopy. Transparent and glass-like plates of silica gel of high purity, after they had been heat-treated at various temperatures below 680 °C, were used for the measurement of OH stretching vibrations ranging from 3100 to 3800 cm−1. These absorption bands were analysed into the several component bands by the simulation method using a Dupont Co. Curve Resolver. The intensity of these bands in area were proportional to the OH concentrations as measured by the thermal method. Each component band disappeared at a temperature which was roughly equal to that obtained from the dielectric and conductivity measurements. From these results, assignment was attempted on the basis of these bands.
ON THE DISSOLUTION VELOCITY OF OXYGEN INTO WATER. PART I
Authors: Miyamoto Susumu , Kaya Tetsuo
Published: July 2006

(1) The oxidation velocity of sodium sulphite solution was observed when air is passed at various velocities.

(2) It was found that the oxidation velocities are independent of the concentration of sodium sulphite and the velocity constant was expressed as a linear function of the velocity of air passed.

(3) The dissolution velocity of oxygen into water when the concentration of oxygen in the surface layer is kept zero, was calculated from the obserbed reaction velocity, and it was found to be expressed as a linear function of the velocity of air passed.

(4) An interpretation of the mechanism of this reaction under the observed conditions was given.

(5) The maximum value of the ratio of the total number of molecules of oxygen which enter into water to the total number of molecules of oxygen which collide with the unit boundary surface per unit of time at 25°C. was calculated from the observed results.
RESEARCHES ON CHEMICAL CHANGES UNDER A STRONG ELECTRIC FIELD
Authors: Aono Takeo
Published: July 2006

1. A new method was devised to apply extremely strong electric force to gases and dielectric liquids, and accelerate their reactions.

2. Using this method, many reactions between gases and liquids under the action of strong electric force were studied. Thereby the effect of temperature elevation and presence of metallic powders (catalyser) were also studied.

3. In connecting with the electric discharge some interesting phenomena were observed.
ON THE DISSOLUTION VOLOCITY OF OXYGEN INTO WATER. PART II
Authors: Miyamoto Susumu , Kaya Tetsuo , Nakata Akira
Published: July 2006

(1) The oxidation velocity of sodium sulphite was observed when the mixture of oxygen and air was passed at uniform velocity under certain conditions.

(2) The observed oxidation velocities were independent of the concentration of sodium sulphite under the present conditions, and the velocity constant was found to be expressed as a linear function of the partial pressure of oxygen passed, as was expected.

(3) The theoretical interpretation on the observed result was given.
Metal Complexes with Amino Acid Amides. IV. Relationship between the CD Spectra of Palladium, Nickel, and Copper Complexes with cis-Bis(amino carboxamidato) metal(II) Type
Authors: Komorita Takashi , Shimura Yoichi
Published: July 2006

Square planar complexes of [ML] type, where M=Pd2+, Ni2+, and Cu2+ for L=N,N′-bis(l-alanyl)-1,3-propanediaminate anion and M=Ni2+ and Cu2+ for L=N,N′-bis(l-alanyl)-1,2-ethanediaminate anion, were synthesized. Their absorption and CD spectra were measured in aqueous, ethanol, and DMF solutions. The results are discussed in comparison with those of cis- and trans-bis(amino carboxamidato)complexes. Definite correspondence is found between the component d-d bands of N,N′-bis(l-alanyl)-1,3-propanediaminatopalladium(II) and those of its nickel analog, in line with a similar correspondence for the corresponding trans-bis(l-amino carboxamidato) complexes. Assignment of the component d-d bands has been reexamined for the copper complexes of bis (amino carboxamidato) type by comparing their CD data with those for the palladium and nickel analogs.
Steric Effect in 3,7-Disubstituted Tropolone. Chemical and Physical Properties of 3-Phenyl- and 3-Isopropyl-7-(2,4,6-cycloheptatrienyl)tropolones
Authors: Tezuka Takahiro , Nozoe Tetsuo
Published: July 2006

The preparation and chemical and spectroscopic properties of 3-phenyl-7-(2,4,6-cycloheptatrienyl)tropolone (1) and 3-isopropyl-7-(2,4,6-cycloheptatrienyl)-tropolone (2) are described. The somewhat unusual properties of 1 and 2 have been discussed in terms of the steric effect of the two substituent groups at positions 3 and 7 in the tropolone ring.
Substituent Effect in the Ionization of cis-2-Substituted 1-Cyclopropanecarboxylic Acids
Authors: Kusuyama Yoshiaki
Published: July 2006

Ten cis-2-substituted 1-cyclopropanecarboxylic acids (substituents: H, CH3, C6H5, CH3O, C2H5O, Cl, Br, CH3CO, CH3OCO, and C2H5OCO) were prepared, and their pKa values were determined in water at 25 °C, along with those of the trans-2-chloro and 2-methoxy derivatives. The pKa values for cis isomers are somewhat larger than those for the corresponding trans isomers, except for the chloro and bromo derivatives. The substituent effects obtained were in the usual order in the sense of the electronic effects, except for the phenyl group, which produced a decrease in acidity relative to the unsubstituted acid. It was shown that the carbon-13 chemical shifts for the methylene carbon of the ethyl group in the ethyl cis-2-substituted 1-cyclopropanecarboxylate obtained in deuteriochloroform gave a reasonable linear relation with the pKa(cis) values.
Synthesis and Thermal Rearrangement of Homobarrelenones. Preparation of Dimethyl 1-Oxo-cis-3a,7a-dihydroindene-3a,7a-dicarboxylates
Authors: Uyehara Tadao , Miyakoshi Shoichi , Kitahara Yoshio
Published: July 2006

The Diels-Alder reaction of five derivatives of 2-methoxytropone with dimethyl acetylenedicarboxylate proceeds regiospecifically giving dimethyl 1-methoxy-2-oxobicyclo[3.2.2]nona-3,6,8-triene-6,7-dicarboxylates, except in the case of 5-isopropyl-2-methoxytropone. The adducts undergo rearrangement selectively to dimethyl 7-methoxy-1-oxo-cis-3a,7a-dihydroindene-3a,7a-dicarboxylates, upon heating under reflux in xylene. Regiochemical aspects of the cycloaddition and mechanistic aspects of the rearrangement are discussed.
Photolyses of Tetraphenylcyclobutanes at 254 nm
Authors: Shizuka Haruo , Seki Ichiro , Morita Toshifumi , Iizuka Takeshi
Published: July 2006

Photolyses of 1,2,3,4-tetraphenylcyclobutanes (TPCB) at 254 nm in hydrocarbon solvents have been studied by means of fluorometry, nanosecond time-resolved spectroscopy, and measurements of the reaction quantum yields. The photolysis of TPCB originates from the S1(π,π*) state to give trans-stilbene nearly concertedly at higher temperatures (>200 K). Significant temperature and cis-effects were observed. The radiationless rate constants for the dissociation (kr) and the other radiationless (kn) processes decreased with lowering temperature. The value of kr for γ-1,t-2,t-3,c-4-TPCB at 300 K, for example, was 4.7 times greater than that for γ-1,t-2,c-3,t-4-TPCB. The Arrhenius parameters of the relaxation processes were also determined. No intramolecular excimer emission was observed.
Conformational Analysis of Intramolecular Fluorescence Quenching of α-(9-Carbazolyl)–ω-[p-(methoxycarbonyl)benzoyloxy]alkanes
Authors: Kanaya Toshiji , Hatano Yoshihiko , Yamamoto Masahide , Nishijima Yasunori
Published: July 2006

Equilibrium distribution of conformations of the series of compounds, α-(9-carbazolyl)-ω-[p-(methoxycarbonyl)benzoyloxy]alkanes in the ground state was calculated to explain the intramolecular fluorescence quenching of these compounds in a rigid medium. It was found that when the radius of active sphere R0 for the intramolecular fluorescence quenching is taken to be 8.8–9.0 Å, the experimentally observed chain length dependence of the fluorescence quenching can be well simulated by this calculation. The active sphere for the dynamic intermolecular fluorescence quenching in solution was also discussed to compare with that of the intramolecular fluorescence quenching.
Film Dichroism. III. Linearly-polarized Absorption Spectra of Highly Symmetric Triphenylmethane Dyes in the Stretched Poly(vinyl alcohol) Films
Authors: Matsuoka Yukio , Yamaoka Kiwamu
Published: July 2006

The linear dichroic absorption spectra of Pararosaniline (PR), Crystal Violet (CV), and Ethyl Violet (EV) were measured in the UV and visible regions by the stretched film technique. Poly(vinyl alcohol) was used as the film matrix. A method, which is expressed in the forms of reduced dichroism and dichroic ratio, was proposed for the analysis of the linear dichroism of disk-like molecules. The dyes PR, CV, and EV were shown to behave like disks regarding their orientation in the polymer matrix. The isotropic absorption spectra of PR, CV, and EV were resolved into the in-plane and out-of-plane polarized components by the reduction procedure. In each isotropic spectrum the out-of-plane component was found to overlap with the intense in-plane component in the UV and visible wavelength regions.
Mechanism for Reaction of p-Nitrotoluene with Sodium Polysulfide to Form p-Aminobenzaldehyde
Authors: Ogata Yoshiro , Kawasaki Atsushi , Sawaki Yasuhiko , Nakagawa Yoshiaki
Published: July 2006

The conversion of p-nitrotoluene to p-aminobenzaldehyde was found to be most effectively done by a mixture of Na2S4 and ca. two equivalents of NaOH to p-nitrotoluene. After examination of probable intermediates, toluidine, p-nitrobenzaldehyde and p-nitrosotoluene were discarded as the intermediate. The reaction of carbanion ArCO\={C}HAr with the sulith the sulfide and the effect of some nitrobenzenes as an electron accepter were examined. These results suggest a mechanism involving a simultaneous oxidation-reduction in a nitrotoluene molecule.
The Structure of the Cyclodextrin Complex. VIII. Crystal Structures of α-Cyclodextrin Complexes with 2-Pyrrolidone and N,N-Dimethylformamide
Authors: Harata Kazuaki
Published: July 2006

Crystal structures of α-cyclodextrin complexes with N,N-dimethylformamide and 2-pyrrolidone were determined by the X-ray method. The pentahydrated crystals of both complexes are orthorhombic, and the space group is P212121 with Z=4. The cell dimensions are a=13.750(1), b=15.318(1), and c=24.544(2) Å for the N,N-dimethylformamide complex, and a=13.852(1), b=15.373(1), and c=24.353(2) Å for the 2-pyrrolidone complex. The structures were determined by assuming the same α-cyclodextrin packing in the crystal as that found in the isomorphous p-nitrophenol complex, and refined by the block-diagonal least-squares method to the final R-values of 0.054 for the N,N-dimethylformamide complex (5151 reflections) and 0.051 for the 2-pyrrolidone complex (5165 reflections). In both complexes, the guest molecules are included in the α-cyclodextrin cavity. The N,N-dimethylformamide molecule is in van der Waals contact with the host α-cyclodextrin molecule, while the 2-pyrrolidone molecule forms a weak N–H…O hydrogen bond with a glycosidic oxygen atom of α-cyclodextrin. The carbonyl oxygen atom of N,N-dimethylformamide and 2-pyrrolidone is hydrogen-bonded to water molecules of hydration located at the primary hydroxyl side of α-cyclodextrin. The tilt-angle of the glucose residue against the plane through six glycosidic oxygen atoms indicates clearly that the macro-cyclic conformation of α-cyclodextrin is affected by the packing as well as the size and shape of the guest molecule. The α-cyclodextrin molecules in the crystal are arranged parallel to the ac plane to form molecular layers. Three water molecules are located near the guest molecule, while the other two water molecules fill the intermolecular space.
Polarized Absorption and Reflection Spectra of the Single Crystals of Benzidine–7,7,8,8-Tetracyano-p-quinodimethane Molecular Complexes
Authors: Yakushi Kyuya , Iguchi Masaaki , Kuroda Haruo
Published: July 2006

Polarized absorption and reflection spectra were observed on the single crystals of the solventfree and solvent containing modifications of benzidine (BD)–7,7,8,8-tetracyano-p-quinodimethane (TCNQ) molecular complex, by using the microspectrophotometers of transmission and reflection types. The absorption spectra obtained by the dispersion analyses of the reflection spectra agreed fairly well with those directly observed by the transmission method. The spectra showed that the BD–TCNQ, complex has non-ionic ground state in all modifications although the intermolecular interaction is considerably strong and is appreciably affected by the inclusion of solvent molecules. In all modifications, the second charge transfer band was confirmed to be polarized in the direction almost perpendicular to the direction of the donor-acceptor stack, while the first charge transfer band is polarized in the direction of the donor-acceptor stack as it is usually found for a typical charge transfer complex. This anomaly of the polarization direction of the second charge-transfer band was concluded to be due to a strong mixing between the charge-transfer excitation and the local excitation associated with TCNQ.
Competitive Redox Reactions at the ZnO Semiconductor Photoelectrode
Authors: Inoue Tooru , Fujishima Akira , Honda Kenichi
Published: July 2006

The study of the photoanodic reaction at the ZnO electrode in an electrolyte solution containing redox agents was carried out by means of the rotating ring-disk electrode technique. The competition reactions between the photocorrosion of ZnO and the oxidation of reducing agents were discussed focusing on the potentials of the electroactive species at the semiconductor-solution interface. The ZnO photoelectrode was stabilized in the course of the oxidation of a strong reducing agent dissolved in a solution.
A Molecular Orbital Calculation of Chemically Interacting Systems. Recombination of Two Methyl Radicals
Authors: Yamabe Shinichi , Minato Tsutomu , Fujimoto Hiroshi , Fukui Kenichi
Published: July 2006

A molecular orbital (MO) approach to a radical-radical reacting system is proposed within the isolated molecule approximation. The interaction energy, ΔW, is defined as the sum of four components, Coulomb, exchange, charge transfer and polarization energies. The four terms are calculated in the recombination of two methyl radicals. The origin of the deformation of methyl radical (D3h→C3v) and the rotational barrier (staggered→eclipsed) in the course of the recombination was found to be the exchange energy caused by the interaction of both doubly occupied MO’s. The difference-density map shows the characteristic role of exchange and charge transfer interactions for charge redistribution.
The Oxidation of Toluene by Cobalt–Copper–Bromide System. A Side-chain Acetoxylation
Authors: Okada Toshihiko , Kamiya Yoshio
Published: July 2006

The liquid-phase oxidation of toluene catalyzed by the cobalt(II) ion and the bromide ion in the presence of the copper(II) ion has been studied. Benzyl acetate was obtained in a good yield (50–70%) with mixed catalysts of metal acetates and sodium bromide in acetic acid at 100–150 °C, accompanied by small amounts of benzaldehyde and benzoic acid. The product distribution was greatly dependent on the NaBr concentration, which can be explained in terms of the high oxidizing ability of the copper(II) ion coordinated by the bromide ion. A synergistic effect was found on the yield of benzyl acetate upon the addition of copper(II) acetate with a high NaBr concentration, the maximum yield being obtained at the Co:Cu:NaBr ratio of 1:1:5–10. A change in the oxygen partial pressure also varied the product distribution, suggesting that the competitive reaction of the copper(II) ion with the oxygen molecule for the benzyl radical was simultaneously taking place at a diffusion-controlled rate. Benzyl acetate was considered to result from the oxidation of the benzyl radical by cop-per(II) bromide and the subsequent solvolysis by acetic acid. The addition of acetic anhydride had a negative effect on the formation of benzyl acetate.
Binary Phase Chlorination of Aromatic Hydrocarbons with Solid Copper(II) Chloride: Reaction Mechanism
Authors: Tanimoto Iwao , Kushioka Keiko , Kitagawa Toyokichi , Maruyama Kazuhiro
Published: July 2006

Anthracene is selectively chlorinated with solid copper(II) chloride to give a quantitative yield of 9-chloroanthracene. The tentative reaction mechanisms so far proposed fail to explain the nonreactivity of some other hydrocarbon homologues, e.g. naphthalene and phenanthrene, toward copper(II) chloride. The present study revealed that the oxidative half-wave potentials (E1⁄2ox) of all reactive hydrocarbon homologues were less than 1.26 V. On the basis of this finding we postulate a reaction mechanism involving one electron transfer from hydrocarbon to copper(II) chloride.
Restricted Rotation Involving the Tetrahedral Carbon. XXVII. Rotamers of 9-(1-Cyano or 1-Methoxycarbonyl-1-methylethyl)triptycene Derivatives Carrying a Substituent in 1-Position
Authors: Otsuka Soichi , Mitsuhashi Tsutomu , \={O}ki Michinori
Published: July 2006

The title compounds were prepared by the reaction between 9-(1-cyano or 1-methoxycarbonyl-1-methylethyl)anthracene and substituted benzynes and their rotational isomers were isolated. The barriers to rotation of these compounds were found to be 35–36 kcal/mol and 32–34 kcal/mol for the processes dl→meso and meso→dl, respectively.
Selective Electrosyntheses on Chemically Modified Electrode. II. Anodic Chlorination of Anisole with Cyclodextrin on Electrode Surfaces and in Solution
Authors: Matsue Tomokazu , Fujihira Masamichi , Osa Tetsuo
Published: July 2006

The anodic chlorination of anisole on an α-cyclodextrin (α-CD) chemically modified electrode via ether linkage (α-CD-CME) and a naked graphite electrode with α-CD or β-CD in solution was studied. In the presence of CD, the p- to o-chloroanisole ratio, formed in the reaction, was higher than that in the absence of CD since o-positions of anisole included in CD are blocked by the inner wall of CD. Especially, α-CD had a profound effect on the p-isomer formation. Increasing the concentration of NaCl added as a supporting electrolyte in the presence of α-CD resulted in a decrease in the ratio because of the inhibition effect of chloride ion on the inclusion of anisole in α-CD, whereas such effect was small in the presence of β-CD. The ratio on α-CD-CME was slightly higher than that on the naked electrode. This indicates that α-CD was introduced on the graphite surface but the surface coverage of α-CD was low, which was in accord with the ESCA results of α-CD-CME.
New Potassium and Ammonium Lead(II) Chromates with a Higher Lead Content and Iso-structural with Potassium Lead(II) Chromate, K2Pb(CrO4)2
Authors: Fukasawa Tsutomu , Iwatsuki Masaaki
Published: July 2006

An unknown yellow precipitate, similar to lead(II) chromate in appearance, has been reported. The precipitate was formed in the detection process of lead(II) ions using chromate ions by a classical qualitative analytical method. The present paper describes the elucidation of the unknown precipitate, and the presence of a series of new chromates iso-structural with the known potassium lead(II) chromate, K2Pb(CrO4)2. The new chromates are explained as new stoichiometric chromates, K4Pb4(CrO4)6 and (NH4)4Pb4(CrO4)6 [=K2Pb2(CrO4)3 and (NH4)2Pb2(CrO4)3], and solid solutions (K, NH4)6−2zPb3+z(CrO4)6 (z=+0.3–+1.2) among the new stoichiometric chromates and the known chromates, K6Pb3(CrO4)6 and (NH4)6Pb3(CrO4)6 [=K2Pb(CrO4)2 and (NH4)2Pb(CrO4)2]. The compositions of the new chromates are dependant on the precipitating conditions. Relationships between compositions, lattice constants, and precipitating conditions are given together with indexed powder diffraction data for references to identification, and the results of thermal analyses.
Asymmetric Benzoin Condensation Catalyzed by Optically Active Thiazolium Salts in Micellar Two-phase Media
Authors: Tagaki Waichiro , Tamura Yoshiharu , Yano Yumihiko
Published: July 2006

Three thiazolium salts, 3-[2-(l-3-p-menthyloxy)ethyl]thiazolium bromide (1), 3-(l-3-p-menthyl)thiazolium halides (2), and 3-(l-3-p-menthyl)-4-methylthiazolium perchlorate (3) have been examined for the catalysis of benzoin condensation in micellar two-phase media. The catalytic activities on the chemical yields of benzoin were observed to be high for 1 and 2 but low for 3. On the contrary, for the asymmetric induction, 3 gave much higher optical purity of 35.3% than in the cases of 1 and 2 (0.8–3.5%). These results are discussed in terms of micellar and conformational effects.
Acidity and Catalytic Activity of Iron(II) Sulfate Heat-treated at High Temperature
Authors: Arata Kazushi , Hino Makoto
Published: July 2006

Acidity and catalytic activity of FeSO4 calcined at 500–900 °C were studied. The product obtained by calcination at 700 °C showed maximum acidity at H0≤1.5 and activity for isomerization of d-limonene oxide, polymerization of isobutyl vinyl ether and dehydration of 2-propanol. When calcined at 750 °C the product showed no acidity or activity.
The Coextraction of Water into Nitrobenzene with Alkali and Alkaline Earth Metal Salts of 2,2′,4,4′,6,6′-Hexanitrodiphenylamine in the Presence of Several Crown Ethers and Cryptands
Authors: Iwachido Tadashi , Minami Masayosi , Kimura Masaho , Sadakane Akira , Kawasaki Mikio , Tôei Kyoji
Published: July 2006

Alkali and alkaline earth metal salts of 2,2′,4,4′,6,6′-hexanitrodiphenylamine (HND) were extracted into nitrobenzene in the absence or presence of several crown ethers or cryptands which differ from one another in hole size. The quantity of water transferred to the nitrobenzene phase was determined by means of the Karl-Fischer method. The NMR and near-infrared spectra show that the coextraction of water is caused by the hydration of the cations. The number of water molecules attached to the cations increases upon going from Cs+ (0.6) to Li+ (5.6) and from Ba2+ (10.5) to Ca2+ (13.0). The complexation between these cations and the crown ethers causes a clear decrease in the hydration number; e.g., in the 1:1 metal–crown ether complexes, more than half of the water molecules are removed, and in the 1:1 metal–cryptand complexes, less than one water molecule remains unremoved. The complexes of a 1:2 stoichiometry are also found; some are stable and carry virtually no water molecules. The number and type of donor atoms have no significant effect on the coextraction of water. The presence of fused benzo rings on the crown ether also has no influence on the number of water molecules.
An ESR Study of N-(Alkylthio)arylaminyls. Substituent Effects on ESR Parameters
Authors: Miura Yozo , Asada Hidetsugu , Kinoshita Masayoshi
Published: July 2006

A series of N-(alkylthio)arylaminyls, ArNSR, were generated by hydrogen-abstraction from N-(alkylthio)anilines or by the photolysis of N,N-bis(t-butylthio)anilines, and were studied by ESR spectroscopy. N-(t-Butylthio)aminyls were fairly long-lived, and their lifetimes were scarcely affected by oxygen. Substituent effects on the ESR parameters were also studied, and the results were compared with those for N-alkoxyarylaminyls.
Bromination of 9-Allyltriptycenes: Bromoolefin Formation and Lifetime of an Intervening Bromonium Ion
Authors: Hatakeyama Shiro , Mitsuhashi Tsutomu , Oki Michinori
Published: July 2006

The bromination of 9-allyl-1,2,3,4-tetrachlorotriptycene affords a mixture of bromoolefins together with a minor quantity of the corresponding dibromide. By the examination of the reactions of model compounds, it is concluded that the first attack of bromine on the olefinic bond takes place in the meso rotamer and the resulted bromonium ion collapses either by attack of the tribromide ion to produce the dibromide or by internal rotation about the C9–Callyl bond followed by attack of the tribromide ion to produce the bromoolefin. Examination of the bromoolefin/dibromide ratios at various temperatures suggests that the activation energy for the attack of the tribromide ion on the bromonium ion is ca. 3 kcal/mol higher than the rotational barrier.
The Low-temperature Photolysis of Diazo Compounds. The Utility of Tertiary Alcohol in Matrix Studies of Carbene Chemistry
Authors: Tomioka Hideo , Miwa Takaaki , Suzuki Shinji , Izawa Yasuji
Published: July 2006

Carbene processes within the t-BuOH matrix at −196 °C were investigated in order to show the utility of the matrix as a tool for the study of carbene chemistry. The photolysis of several aryldiazomethane derivatives in the t-BuOH matrix gave the olefinic dimer as the main product, probably arising from a combination of two triplet arylcarbenes in the aggregate of molecules. The similar photolysis of other diazo compounds (e.g., N2CHCOR, R=OR′, NEt2, and Ph) resulted in no detection of the olefinic dimer. This was explained in terms of the structural effect on the ground-state multiplicity of carbene. The photolysis of Ph2CN2 in t-BuOH containing 5% EtOH at −196 °C gave almost exclusively O–H and C–H insertion products with the solute alcohol at the expense of the O–H insertion product with the host, i.e., Ph2CHOBut, which was the major product in the liquidphase photolysis. This is ascribable to the co-aggregation of the carbene precursor with the solute alcohol because of the relatively large guest hole provided by the bulky tertiary alcohol matrix. A more general utility of this matrix was shown in the reaction of Ph2C with Ph2CO to give oxirane, in which the intervention of carbonyl ylide was demonstrated at low temperatures.
Calculations of g Tensors and Hyperfine Splitting Tensors for Molecules in Their Triplet States
Authors: Morikawa Tetsuo , I’Haya Yasumasa J , Nakano Junji
Published: July 2006

The g tensors and hyperfine splitting (hfs) tensors of simple organic radicals in their triplet states have been calculated by using an all valence electron SCF MO method with a first order perturbation treatment. The molecular orbital spin density is partitioned into the σ- and π-electron spin delocalization (SD) terms and the rest terms of spin polarization (SP) which arise from the CI effect. The g tensors for CH2 and several other carbenes which have triplet ground states and for formaldehyde in its nπ* and nσ* excited triplet states are evaluated. The calculated α-proton hfs constants of CH2 contributing from the π orbital well compare with the observed hfs constants of the triplet naphthalene and the doublet malonic acid radical. The anisotropic carbon-13 hfs constants of CH2 are determined almost completely by the SD contribution and their absolute values are in good accord with those observed for CD2. Contribution of the SP terms to the isotropic hfs constant is found to be fairly large. Prediction of the hfs constants in CF2 and CHF is made.
Conformations of Acetanilide and Related Compounds Studied by Ultraviolet Photoelectron Spectroscopy
Authors: Nakagaki Ryoichi , Kobayashi Tsunetoshi , Nagakura Saburo
Published: July 2006

Conformations of acetanilides were studied by UPS in the vapour phase. The dihedral angle, θ, between the amide group and the phenyl group was evaluated from the difference in the vertical ionization energy, ΔEiv, between the two MO’s, the anti-bonding and bonding type combinations of the benzene ring e1g(S) orbital and the highest occupied π orbital of the amide group. The steric inhibition of conjugation due to N-methylation is larger than that due to ortho-methylation. For this series of compounds, ΔEiv is directly proportional to cos θ and this simple relationship is useful for the rough estimation of θ.
SORPTION OF GAS BY MINERAL. III. SILICIC ACID MINERALS
Authors: Sameshima Jitsusaburo
Published: July 2006

1. Sorption of ammonia by dehydrated materials of chalcedonies, opal, diatomaceous earth, natural silica gels and siliceous sinter have been measured.

2. All these substances sorb considerable amounts of ammonia at ordinary temperature.

3. The sorption velocity can be expressed by the equation

x=Klogt+k,

where x is the sorption amount at time t, and K and k are the constants.
ON THE UNSAPONIFIABLE MATTER OF CALAMARY OIL
Authors: Tsujimoto Mitsumaru
Published: July 2006

(1) The unsaponifiable matter of calamary oil contained 48% of cholesterol.

(2) Besides cholesterol, the presence -of cetyl, batyl and selachyl alcohols has been confirmed. Oleyl and chimyl alcohols were probably present. A small amount of the alcohols of higher unsaturation appeared also to be present.

(3) The occurrence of the alcohols of the selachyl alcohol group (monoglyceryl ethers) in calamary oil indicates the wide distribution and vital importance of these compounds as constituents of liver oils of various marine animals.
ON THE DIBASIC ACIDS IN JAPAN WAX
Authors: Tsujimoto Mitsumaru
Published: July 2006

(1) As “japanic acid” of Geitel and van der Want appears not the only dibasic acid in Japan wax, this name has been reserved for a while, and the expression of the “Japan wax dibasic acids” or more simply the “dibasic acids” is used in this paper.

(2) Basing on the difficult solubility of the dibasic acids in petroleum ether, a method for their approximate determination has been proposed. The results obtained by this method show that the content of the dibasic acids in the mixed fatty acids of Japan wax amounts to 5–6%, which are far greater than hitherto considered.

(3) For the preparative separation of the dibasic acids, the lead salt precipitation method and the ester distillation method have been found to be most convenient.

(4) As the results of the chemical examination of the dibasic acids, it has been concluded that the main constituent of the acids is heneicosane dicarboxylic acid, C23H44O4, but probably eicosane dicarboxylic acid, C22H42O4 also occurs in a fair proportion.

(5) As a peculiar property of the dibasic acids, it has been found that the comparatively small addition of them to fatty and waxy substances makes the crystalline structure of these substances finer and more opaque, and at the same time gives certain coherency and tenacity.

(6) The characteristic property of Japan wax that it may be kneaded to a “mochi”-like mass without adhering to the fingers is due to the presence of the glycerides of the dibasic acids.
ON THE DISSOLUTION VELOCITY OF OXYGEN INTO WATER. PART IV
Authors: Miyamoto Susumu , Nakata Akira
Published: July 2006

(1) The oxidation velocity of sodium sulphite was studied, when the condition is satisfied, under which the concentration of oxygen in the boundary surface layer is always zero. The oxidation velocity is independent of the concentration of sodium sulphite and is proportional to the boundary surface area.

(2) The theoretical considerations on the observed oxidation velocity was given.

(3) The assumption that only the molecule of oxygen, whose component of velocity vertical to the boundary surface is greater than a threshold value u0 is able to enter into the liquid phase, was given, and the values of u0 were calculated at 15°C., 25°C. and 35°C. from the experimentally obtained result.

The calculated value of u0 is 1.65×105 cm. per sec. and is independent of the temperature within the observed region.
Mössbauer Emission Spectroscopy of 57Fe Arising from 57Mn in Metal and Oxides of Chromium
Authors: Nakada M , Watanabe Y , Endo K , Nakahara H , Sano H , Mishima K , Kubo M K , Sakai Y , Tominaga T , Asai K , Iwamoto M , Kobayashi Y , Okada T , Sakai N , Kohno I , Ambe F
Published: July 2006

The chemical states of 57Fe arising from 57Mn produced by the 54Cr (α, p) 57Mn reaction in the metal and oxides of chromium were studied by 57Fe Mössbauer emission spectroscopy. In chromium metal, all of the 57Fe atoms were found at substitutional sites. Both the iron(II) and iron(III) species were observed in Cr2O3, while only iron(III) ions were detected in CrO3.
Extractive Separation and Photometric Determination of Vanadium with Benzoylacetone
Authors: Chauhan Rakam Singh , Kakkar Lajpat Rai
Published: July 2006

A very simple and rapid method for the extractive separation and photometric determination of vanadium is worked out using benzoylacetone as a complexing reagent for V(III), produced on reduction of V(V) with sodium dithionite in dil acetic acid medium. The colored complex is extractable into benzene. The interfering effect of a large number of elements is eliminated completely leading directly to the determination of the metal ion present in traces in samples. The method is applicable to the analysis of different technical samples and the results obtained are highly reproducible. Metal to ligand ratio in the extracted species is determined as 1 : 3.
Photocyclization of Diphenylamine Studied by Time-Resolved Thermal Lensing. Heat of Reaction, Energetics, and Reactivity of Intermediates
Authors: Suzuki Tadashi , Kajii Yoshizumi , Shibuya Kazuhiko , Obi Kinichi
Published: July 2006

The time-resolved thermal lensing (TRTL) technique was employed to study the photocyclization of diphenylamine (DPA) to form intermediate 4a,4b-dihydrocarbazole (DHC) in methanol solution at room temperature. The heat of reaction, ΔH, was determined to be (2.6 ± 0.2) × 102 kJ mol−1 (1DPA → 1DHC): The reaction proceeds endothermically. The ring closure step proceeds on the triplet surface (3DPA* → 3DHC*). These triplet states are found to be isoenergetic by analyzing the time evolution of the TRTL signal. 3DHC* is located at 21 kJ mol−1 above 1DHC. Furthermore, two-color laser flash photolysis experiments have revealed that the photoexcitation of intermediate 1DHC leads to the recovery of parent DPA and therefore inhibits the formation of carbazole.
Ascorbic Acid: A Jaffé Interference
Authors: Viraraghavan Saroja
Published: July 2006

The effects of ascorbate, the interference of the Jaffé reaction was individually studied by polarography, spectrophotometry, and thin-layer chromatography. Ascorbate was incubated in 28.4 mmol dm−3 picrate blank solution in 0.51 mol dm−3 NaOH at 25.00 ± 0.02 °C and the reactivity of test solution containing ascorbate : picrate was investigated. Picramic acid formed in all ascorbate: 28.4 mmol dm−3 picrate test solutions which explained the observed positive interference of ascorbic acid. No fluorescent product was formed in ascorbate : picrate test solutions. The reactivity of ascorbate : picrate test solutions confirmed that ascorbate was a powerful reducing agent. 2-Furaldehyde which has been listed as one of the degradation products of ascorbic acid, is not identified under the experimental conditions.
One-Pot Synthesis of Optically Active Cyanohydrin Acetates from Aldehydes via Quinidine-Catalyzed Transhydrocyanation Coupled with Lipase-Catalyzed Kinetic Resolution in Organic Solvent
Authors: Inagaki Minoru , Hatanaka Akihiko , Mimura Mitsuo , Hiratake Jun , Nishioka Takaaki , Oda Jun’ichi
Published: July 2006

A novel one-pot synthetic method was developed for the preparation of optically active cyanohydrin acetates. Racemic cyanohydrins were generated from aldehydes and acetone cyanohydrin by quinidine-catalyzed transhydrocyanation, and the resulting cyanohydrins 2a–j were then acetylated by lipase in a stereoselective manner using isopropenyl acetate as an acylating regent. A variety of aldehydes 1a–j were successfully transformed into the corresponding cyanohydrin acetates 3a–j having 47–95% e.e. without isolating the unstable cyanohydrins 2. Moreover, the reversible nature of base-catalyzed transhydrocyanation allows for in situ racemization of the unreacted cyanohydrins and concurrent kinetic resolution by lipase enabled the preparation of (S)-3b–d with 40–82% e.e. in more than 50% yield. Polymer-supported cinchona alkaloid was also used as a catalyst for this one-pot reaction and showed the comparable chemical and optical yield to that for the soluble monomeric alkaloid. The insoluble polymer and lipase were recovered by filtration and found to have almost the same catalytic activity even after four times of reuse.
FeS2-Catalyzed Hydrocracking of α,ω-Diarylalkanes
Authors: Wei Xian-Yong , Ogata Eisuke , Niki Etsuo
Published: July 2006

Hydrocracking reactions of α,ω-diarylalkanes (DAAs) were carried out in the presence of FeS2 catalyst to examine the structural effect of DAAs on the reactivities of DAAs toward hydrocracking. Reactivities and reaction pathways of DAAs were found to depend not only on aromatic ring size, but also on the number of methylene between aromatic rings. Diarylmethanes were hydrocracked via Car–Calk bond scission, while the Car–Calk bond scission for 1,2-diarylethanes and 1,3-diarylpropanes seemed to be very difficult. These results could be interpreted by the hydrogen-accepting abilities of the ipso-carbons in the substrates and the resonance stabilities of the resulting arylalkyl radicals.
Crystal Structure of N-Cinnamoyl-8-oxa-6-azabicyclo[3.2.1]octan-7-one
Authors: Yamane Takashi , Ashida Tamaichi , Hashimoto Kazuhiko , Sumitomo Hiroshi
Published: July 2006

The crystal structure of the title compound has been determined in order to study the structure-reactivity relationship of a bicyclo compound. C15H15O3, M 257.29, monoclinic, space group P21/a, a = 24.122(6), b = 6.990(2), c = 7.800(2) Å, β = 94.27(2)°, V = 1311.5(6) Å3, Z = 4, Dx = 1.304 g cm−3, μ = 7.56 cm−1 for Kα. The final R-value is 0.062 for 1948 reflections. The molecular structure is essentially the same as that of the N-benzoyl derivative of the bicyclo compound. An elongation of the C–N bond distance in the lactam-amide moiety, which had been found in the N-benzoyl derivative, was observed and compared with that in the unmodified bicyclo compound. There seems to be little extension of the conjugation of the olefinic group to the carbonyl or phenyl groups in a cinnamoyl moiety, according to the C=C and Csp2–Csp2 distances.
The Binding Characteristics of Sodium Decyl Sulfate to Poly(l-ornithine) with 1-Alkanesulfonate Counter Ions
Authors: Satake Iwao , Uchino Koichiro , Hayakawa Katumitu , Maeda Tamaki
Published: July 2006

The study was made of the binding isotherms of decyl sulfate ion to poly(l-ornithine) with 1-alkanesulfonate counter ions of the chain length (n) from 3 to 7. The coil to helix transitions of polypeptide chain in these syctems were also studied. Although the binding cooperativity decreased rapidly with increasing n, the conformational change was insensitive to n.
Selectivity in Catalytic Dehydrogenation with Active Manganese Dioxide
Authors: Kimura Takahide , Fujita Mitsue , Sohmiya Hajime , Ando Takashi
Published: July 2006

The selectivities in the competitive dehydrogenation of alcohols, such as benzhydrol and cinnamyl alcohol, with active manganese dioxide under catalytic conditions are different from those under the usual conditions.
Stability and Resonance Energy of Azulenequinones and the Rule for Topological Charge Stabilization
Authors: Kurihara Teruo , Ishikawa Sumio , Nozoe Tetsuo
Published: July 2006

An examination was made of the stability and formation pathways of azulenequinones produced by oxygenation in terms of Aihara’s graph theory of aromaticity and Gimarc’s TCS rule. In view of the TCS rule, the oxygen molecule in autoxidation first attacks C-1 of the azulenes, followed by the another oxygen molecule attacking at position n in 1-carbonylated azulenes to give azulenequinones.
A New Ketyl Radical Probe. Dehalogenation of o-Halobenzophenone
Authors: Yamataka Hiroshi , Yamaguchi Kazuhiko , Takatsuka Tsutomu , Hanafusa Terukiyo
Published: July 2006

The reactions of o-, m-, or p-bromobenzophenone and o-iodobenzophenone with various Grignard reagents were carried out in diethyl ether at 0 °C. The product analysis showed that these halobenzophenones can be a good chemical probe to evaluate the electron-transfer ability of nucleophiles to the aromatic ketones.
Fluorescence Quenching of Europium(III) by Heteronuclear Complex Formation with Copper(II) or Nickel(II)
Authors: Sakamoto Masatomi , Hashimura Masayuki , Nakayama Yusaku , Matsumoto Akira , Okawa Hisashi
Published: July 2006

Fluorescent spectra of the mononuclear europium(III) complex, Eu(H2 fsaen) (NO3)·5H2O, and the heteronuclear complexes MEu(fsaen) (NO3)·nH2O (n = 4 for M = Cu(II) and n = 6 for M = Ni(II)), were compared, where H4 fsaen is a binucleating ligand, N,N′-bis (3-carboxysalicylidene)ethylenediamine. It was found that the fluorescent bands of Eu(III) observed for the mononuclear complex were significantly quenched on forming binuclear complexes.
Direct Nebulization of Sample Solution Containing Reductant for the Determination of Mercury by Inductively Coupled Plasma-Atomic Emission Spectrometry
Authors: Nakahara Taketoshi , Wasa Tamotsu
Published: July 2006

In order to enhance the sensitivity of mercury, the most effective reductant, tin(II) chloride was added to a mercury solution, and the mixture was immediately introduced into the plasma through a conventional pneumatic nebulizer. The attainable detection limit for mercury was inproved from 79 ng ml−1 in the untreated solutions to 1.3 ng ml−1 when tin(II) chloride was added. The present method was successfully applied to the determination of trace concentrations of mercury in several samples of waste water.
A New Estimate of Ionic Values of Viscosity B-Coefficient, NMR B′-Coefficient and the Ion-Solvent Interactions at Extended Temperatures in Aqueous Solutions
Authors: Bhattacharyya Moni Mohan
Published: July 2006

New estimates of ionic viscousity B-coefficient and NMR B′-coefficient have been obtained in aqueous solutions over the temperature range 0 to 95 °C by a recently developed method. The derived values for the alkali metal and halide ions have been compared with the existing ones and the discrepancies discussed. Temperature effect on the two coefficients for the simple inorganic ions has been satisfactorily discussed using the concept of the Frank and Wen model. Energy of activation for viscous flow has also been calculated using the Eyring model and three different values are obtained for each ion over the temperature range studied.
Template Synthesis and Structure of a Dinuclear Lead(II) Complex of Novel Macrocycle Derived from 2,6-Diformyl-4-methylphenol and 1,9-Diamino-3,7-diazanonane
Authors: Motoda Ken-ichiro , Sakiyama Hiroshi , Matsumoto Naohide , Okawa Hisashi , Kida Sigeo
Published: July 2006

The reaction of 2,6-difomyl-4-methylphenol and 1,9-diamino-3,7-diazanonane in methanol in the presence of lead(II) ion forms a dinuclear lead(II) complex of a very rare macrocycle containing hexahydropyrimidine rings. The structure of the complex is determined by single crystal X-ray method.
Syntheses and Properties of Heterodinuclear μ-Ethynediyl Complexes Containing Palladium and Platinum
Authors: Onitsuka Kiyotaka , Joh Takashi , Takahashi Shigetoshi
Published: July 2006

Heterodinuclear μ-ethynediyl complexes Cl(R3P)2MC≡CM′(PR3)2Cl (3) (M = Pt, M′ = Pd; R = Me, Et, n-Bu) were prepared by the reactions of chloroethynylbis(trialkylphosphine)platinum (1) with dichlorobis(trialkylphosphine)palladium (2) in the presence of CuCl catalyst. These complexes were fully characterized by mass, 13C{1H}, and 31P{1H} NMR spectroscopies.