bluuebunny/crossref_metadata_2025 huggingface dataset:
Aromatic Arylation with Aryl Radicals. III. Gomberg Reaction in Dimethyl Sulfoxide
Authors: Kamigata Nobumasa , Kurihara Teruyoshi , Minato Hiroshi , Kobayashi Michio
Published: July 2006

Benzenediazonium tetrafluoroborate in dimethyl sulfoxide decomposed instantaneously with evolution of nitrogen upon addition of a dimethyl sulfoxide solution of choline or tetramethylammonium hydroxide. Orientations and partial rate factors for the phenylation of substituted benzenes indicated that the phenylating agent is not phenyl cation but phenyl radical. Hammett’s plots of partial rate factors for meta and para substitutions were good straight lines with ρm=0.34, ρp=1.63 (in choline) and ρm=0.48, ρp=1.69 (in tetramethylammonium hydroxide solutions). Decomposition of benzenediazonium tetrafluoroborate by tetramethylammonium hydroxide in aqueous solution was also studied, and the orientation and partial rate factors for the phenylation of substituted benzenes were determined.
Infrared Spectra and Normal Vibrations of N,N-Dimethylformamide and N,N-Dimethylthioformamide
Authors: Durgaprasad G , Sathyanarayana D N , Patel C C
Published: July 2006

The infrared spectra of N,N-dimethylformamide (DMF) and N,N-dimethylthioformamide (DMTF) have been investigated in the range 4000–250 cm−1. Assignment of the frequencies of DMF has been made on the basis of normal coordinate analysis for DMF, DMF-15N, and DMF-d7 using Urey-Bradly, modified Urey-Bradley, and symmetrized valence force fields. Calculations have been extended to N,N-dimethylthioformamide and N,N-dimethylselenoformamide, using the Urey-Bradley and symmetrized valence force fields. The assignments for DMF from the modified Urey-Bradley field are found to be more satisfactory. The frequency shifts on isotopic substitution and on complexation have been explained. The results of the calculations are discussed in comparison with other related molecules.
The Hydrogenation of Aniline over Supported Rhodium-Palladium Alloy Catalysts
Authors: Ikedate Kazue , Suzuki Sadao
Published: July 2006

The hydrogenation of aniline was investigated in the temperature range from 30° to 50°C over Rh-Pd alloy catalysts supported on activated carbon. The reactions were mainly carried out in acetic acid at an atmospheric pressure of hydrogen. The activity per unit weight of the catalysts was measured and plotted for the alloy composition. It showed a maximum at 75–85 wt% Rh. However, the activity per unit of surface area showed a maximum at about 25 wt% Rh, and the minimum activation energy of this reaction was observed at the same composition. The relationship between the selectivity and the alloy composition was also studied. The maximum selectivity to dicyclohexylamine was observed at 20–30% Rh, while the maximum formation of N-phenylcyclohexylamine appeared at 50–60% Rh. However, the selectivity to cyclohexylamine showed a minimum at about 25% Rh. The initial rates of the formation of cyclohexylamine and N-phenylcyclohexylamine were measured and plotted for the catalyst composition. The maximum activity was observed at about 85 wt% Rh for the formation of cyclohexylamine and at 50–60% Rh for the formation of N-phenylcyclohexylamine. Then the ratios of the two simple reaction rates were calculated. At a higher Rh content, (above about 25% Rh), the selectivity increased as the ratio increased. The reaction over the catalysts prepared by different methods and the hydrogenation of aniline in cyclohexane were also investigated.
The Electrolytic Conductances of Bis(halogenoacetato)bis(ethylenediamine)cobalt(III) Ions in Water
Authors: Yokoi Masatoki , Kuroda Kashiro
Published: July 2006

The electrolytic conductances of bis(halogenoacetato)bis(ethylenediamine)cobalt(III) perchlorate, [Co(halac)2(en)2]ClO4 where Hhalac=CH3CO2H, CH2ClCO2H, CHCl2CO2H, CCl3CO2H, and CF3CO2H were measured in water at 25°C. The equivalent conductances of the solutions (c=10−3–10−4 mol/l) were obtained from the conductance kinetic runs by extrapolating conductances to time zero. The ionic equivalent conductances of the complex ions were 21.5–17.2 ohm−1cm2eq.-−1. and decreased with the increase of the chlorine content in the chloroacetato ligands. Little differences in the ionic equivalent conductances were observed between a pair of cis and trans isomers. The rate constants of the first order aquation of the complexes were estimated.
Two Types of Complexes of o-Phenylenediamine with Tetracyanoquinodimethane
Authors: Ohmasa Masatake , Kinoshita Minoru , Akamatu Hideo
Published: July 2006

o-Phenylenediamine and tetracyano-p-quinodimethane (TCNQ) were shown to form two types of solid complexes with compositions of 1 : 1 and 2 : 1. The 2 : 1 complex is essentially of ionic type, while the 1 : 1 complex is characterized as of non-bonding type from the analysis of its infrared absorption spectrum. It was shown that the difference in type is reflected on the magnetic and electrical properties of these complexes. The ESR absorption or the spin concentration of the 1 : 1 complex changed irreversibly with grinding or heat-treatment (70°C), while no appreciable change was observed in the 2 : 1 complex with these treatments. The electrical resistivity is lower for the 1 : 1 complex than the 2 : 1 complex by a factor of 102. From these observations, it is considered that the ground state electronic structure of the 1 : 1 complex is in a similar situation to those of diaminopyrene-chloranil and benzidine-TCNQ complexes.
The Flow Properties of Hydrophilic Latexes Thickened with Alkali
Authors: Ito Yoshio , Shishido Shunsuke
Published: July 2006

This paper has aimed at the revelation of the thickening mechanism of a latex on the addition of alkali. Experiments have been made on two kinds of latexes dialyzed thoroughly, i.e., the butadiene–methyl methacrylate copolymer latex and the butadiene-methyl methacrylate–methacrylic acid copolymer latex. The degree of the swelling of the latex particles on the addition of alkali has been correctly obtained and has been connected with the thickenability of the latex. The results provide a more rigorous description than Wesslau’s suggestion that the thickening of a latex on the addition of alkali is ascribed to the swelling of the latex particles alone. The reason why NH4OH is a proper thickener is presented, and the most suitable amount of alkali for the thickening of a latex is discussed.
Studies on Aminosugars. XXIX. Syntheses of Nucleosides of 3-Amino-3-deoxy-3-C-hydroxymethyl-β-d-ribofuranose
Authors: Yanagisawa Hiroaki , Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

Reduction of 3-acetamido-3-C-carboxy-3-deoxy-1,2-O-isopropylidene-α-d-ribofuranose-y-lactone (1) with lithium aluminum hydride or sodium borohydride followed by acetylation gave 3-acetamido-3-C-acetoxymethyl-5-O-acetyl-3-deoxy-1,2-O-isopropylidene-α-d-ribofuranose (2). Hyrdolysis of 2 followed by N-phthaloylation and O-acetylation gave 3-C-acetoxymethyl-5-O-acetyl-3-deoxy-1,2-O-isopropylidene-3-phthalimido-α-d-ribo-furanose (7), which was acetolyzed and chlorinated to give acylglycosyl chloride (9). Condensation of 9 with 6-benzamidopurine followed by aminolysis afforded 9-(3′-amino-3′-deoxy-3′-C-hydroxymethyl-β-d-ribofuranosyl) adenine (11). 6-dimethylaminopurine, guanine, cytosine and uracil derivatives were similarly synthesized.
Studies on Hetero-Cage Compounds. II. pKa Studies on the 3,10-Diazabicyclo[4.3.1]decane System
Authors: Sasaki Tadashi , Egughi Shoji , Kiriyama Tsutomu
Published: July 2006

The pKa values of pseudopelletierine (1), 10-methyl-3,10-diazabicyclo[4.3.1]decan-4-one (2), 10-methyl-3, 10-diazabicyclo[4.3.1]decane (3), 6,8-exo-ethanopseudopelloetierine (4), 7,9-exo-ethano derivatives 5 and 6 of 2 and 3 were measured potentiometrically in water-methyl cellosolve (20 : 80 v/v) at 20°C. The conformational problems in the 3,10-diazabicyclo[4.3.1]decane system were discussed based on the observed pKa′ (pKmcs) values. The characteristic conformational behavior of the monocation (7) of 3 was suggested by the higher value of its pKmcs than of 6.
The Synthesis and Photo Reaction of 7,11-Dimethyl-1,6,10-dodecatrien-3-one
Authors: Kato Tadahiro , Maeda Hideo , Tsunakawa Mitsuaki , Kitahara Yoshio
Published: July 2006

For the purpose of constructing a pinene skeleton (I), a promising intermediate for the synthesis of bergamotenes (III), the vinyl ketone (II), was synthesized from geranyl bromide (IV) by the application of Meyer’s method, followed by a Grignard reaction with vinylmagnesium bromide and subsequent oxidation. The irradiation of II in absolute ether afforded an unexpected keto ether (X) in a low yield; it was characterized by means of a deuterium-exchange reaction and physical methods. No other product except X was isolated from the photoreaction mixture of II.
Studies on the Electronic Spectra of the Semiquinones of Anthracene and Its Related Heterocycles. II
Authors: Masuhara Hiroshi , Okuda Michio , Koizumi Masao
Published: July 2006

The electronic structures of semiquinones of anthracene and its related heterocycles were calculated, using the open shell SCF procedure combined with configuration interaction calculations. A general classification and some peculiarities of the observed absorption spectra of these semiquinones can be readily explained by the present theoretical results. The effects of resonance integral and configuration interactions were examined in detail. The results obtained by considering the effect of hyperconjugation were added.
The Formation of κ and κ′-Al2O3 from the Dehydration of Tohdite 5Al2O3·H2O
Authors: Okumiya Masataro , Yamaguchi Goro , Yamada Osamu , Ono Shuichiro
Published: July 2006

The dehydration of tohdite 5Al2O3·H2O is well followed by means of the single-crystal electron-diffraction patterns, the X-ray powder patterns, differential thermal analysis, and the measurement of the density. Thermogravimetric measurements were also performed, both under a normal atmosphere and in a high vacuum. Just after the dehydration, an unstable intermediate phase was obtained; it was denoted as κ′-Al2O3(from tohdite). The mechanism of the transformation series:

tohdite→κ′-Al2O3→κ-Al2O3→α-Al2O3

was discussed, and some basic data to serve as clues to elucidate the crystal structure of κ′- and κ-Al2O3 were obtained.
Study of Acidity Constants of 3-, 4-, 5-, and 6-Chloro-o-toluidinium Ions in Aqueous Solution and Related Thermodynamic Quantities. I
Authors: Gandhi A H , Patel S R
Published: July 2006

The acidity constants of anilinium, simple and 3-, 4-, 5-, and 6-chloro-o-toluidinium ions have been studied at seven different temperatures by pH metry in aqueous solution and correlated using the relation lnK=A+BT+CT2. The values of ΔG, ΔH, ΔS, and ΔCp have been calculated at different temperatures. The possibility of the additivity in the thermodynamic quantities of these disubstituted anilinium ions has been examined. Hammett type equation has been developed to correlate the acidity constant of these ions at 25°C. Attempt has been made to explain the trends in the thermodynamic quantities of these ions in terms of polar, steric, and solvent effects.
Thermal and Photolytic Decompositions of Azobis(2-phenylthio)-2-propane
Authors: Ohno Atsuyoshi , Kito Noboru , Ohnishi Yutaka
Published: July 2006

Thermal and photolytic decompositions of azobis(2-phenylthio)-2-propane have been studied. The reaction mechanisms have been discussed on the basis of products. Almost all reactions of 2-phenylthioprop-2-yl radicals produced from the azo compound photolytically proceed with in-cage processes. The ratio, disproportionation/dimerization, predicts qualitatively that the radical center of the free radical is more electronegative than that of the corresponding oxygen analog.
The Reaction of α-Oxo Acids with N-Phenyltriphenylphosphinimine
Authors: Shin Chung-gi , Ando Hiroki , Yoshimura Juji
Published: July 2006

The reaction between ethyl α-oxocarboxylate and N-phenyltriphenylphosphinimine gave a mixture of ethyl α-phenyliminocarboxylate (IVa–f) and the tautomeric isomers (Va–f) in good yield. IVa and Va derived from ethyl pyruvate was converted gradually into 3-anilino-5-ethoxycarbonyl-5-methyl-1-phenyl-Δ3-pyrrolin-2-one (VIIa) on standing at room temperature. The free acid of IVa and Va prepared by the same method could not be purified, but a small amount of 3-anilino-5-methyl-l-phenyl-Δ3-pyrrolin-2-one (IX) was obtained from the reaction mixtures. In the reaction of aniline and pyruvic acid, α,γ-dianilino-γ-carboxy-α-methyl-γ-butyrolactone (XII) was obtained in the neutral reaction condition and 4-anilino-2-phenyliminopentanoic acid (XIV) in basic condition. The structure of the products was proved by NMR and IR spectrum, and the reaction courses were discussed.
Solvent Effects on the Spin-Lattice Relaxation Times and Chemical Shifts of N-Methylacetamide and N,N-Dimethylacetamide
Authors: Sato Kazuo , Nishioka Atsuo
Published: July 2006

The spin-lattice relaxation time T1 and chemical shift of N-methylacetamide (NMA) and N,N-dimethylacetamide (DMA) were measured in D2O and CCl4 solutions. In D2O solution, it has been found that the weak interamide hydrogen bonding of NMA does not affect the spin-lattice relaxation entirely, and the molecular motion of NMA and DMA is almost identical. However, quite different results were obtained for CCl4 solution. The molecular association of NMA in CCl4 solution is strong enough to exhibit appreciable effects on spin-lattice relaxation. The life time of the associated molecules has been estimated to be longer than 10−10–10−11 sec. The association of DMA at high concentration region in CCl4 could be verified from the concentration dependence of the spin-lattice relaxation rate as well as chemical shift.
Reaction of Aromatics with Thallic Salts—Preparation of Arylthallic Compounds
Authors: Ichikawa Katsuhiko , Uemura Sakae , Nakano Takeshi , Uegaki Eizo
Published: July 2006

Arylthallic acetate perchlorate monohydrates, Ar-Tl(OAc)(ClO4)·H2O, were obtained as the major products of the reaction between thallic acetate and aromatics in acetic acid containing perchloric acid. As the minor products, various types of oxidation products including oxidative coupling were obtained. Reactivity order of the aromatics and the isomer distributions in the products were the same as those in the usual electrophilic aromatic substitution. With thallic nitrate, sulfate, and chloride, no arylthallic compounds could be obtained.
Studies on Cobaloxime Compounds. I. Synthesis of Various Cobaloximes and Investigation on Their Infrared and Far-Infrared Spectra
Authors: Yamazaki Noboru , Hohokabe Yorikatsu
Published: July 2006

Cobaloximes with the general formula: [CoX(DH)2B] or [RCo(DH)2B] (X: Cl, CN. R: Alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, benzyl, or hydroxypropyl. DH: Dimethylglyoximato monoanion. B: Bases such as water, nicotinamide, p-toluidine, pyridine, γ-picoline, imidazole, or 4-vinylpyridine), and polymeric cobaloximes with the general formula: [Co(OH)(DH)2(Copoly–AM-VPy)] (Copoly–AM-VPy: a low molecular weight copolymer of acrylamide and 4-vinylpyridine), were synthesized and their infrared and far-infrared spectra were examined. The frequency shifts by changing the axial ligands were discussed.
Emission Spectra Obtained by Low Energy Electron Bombardment of Methane and Chlorinated Methanes
Authors: Ogawa Teiichiro , Fujita Iwao , Hatada Motoyoshi , Hirota Kozo
Published: July 2006

Spectroscopic studies of a molecular beam bombarded by a low energy electron beam were carried out for several simple organic molecules. The collision chamber resembled the ionization chamber of a mass spectrometer, and the electrons were accelerated at about 270 V. The spectrum of methane showed lines of excited hydrogen atoms and bands of excited CH radicals. The spectra of chlorinated methanes showed lines of excited chlorine atoms and bands of excited hydrogen chloride positive ions (HCl+*) in addition. Even the spectrum of a mixture of methane and carbon tetrachloride revealed bands of HCl+*. Dependence of emission intensities on target currents and gas pressures indicated the origin of the excited hydrogen atoms and CH radicals to come from direct fragmentation and the excited HCl+ ions from a bimolecular process.
Rapid Extraction of Antimony with Tributyl Phosphate. Direct Photometric Determination with Brilliant Green
Authors: Yadav A A , Khopkar S M
Published: July 2006

A new method is developed for the rapid extraction and direct photometric determination of antimony. With 20% TBP-toluene 3 to 15 μg of antimony is extracted from 2m hydrochloric acid containing 1 m magnesium chloride. From the organic phase, antimony is directly determined photometrically at 640 nm as its complex with brilliant green. Antimony can be selectively extracted in the presence of a large number of cations and anions. The total operation requires only 20 min.
Syntheses and Properties of Copper(II), Nickel(II), and Cobalt(II) Complexes of Alkylthioglycolic Acids
Authors: Ouchi Akira , Takeuchi Toshio , Ohashi Yayoi
Published: July 2006

Copper(II), nickel(II), and cobalt(II) complexes of alkylthioglycolic acids, R·S·CH2COOH (where R=ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl), were synthesized. Except for some copper complexes, these are new compounds. The attempt to synthesize the solid zinc complexes by the same method has not yet been successful. The relative stabilities of these complexes in the solid state seem to be Zn(II)<Co(II), Ni(II)<Cu(II), considering the yield of the syntheses of the products as well as the solvolizing tendency of the complexes. The nickel and cobalt complexes are expected to be in an octahedral form from the magnetic moments as well as from their electronic spectra. The relation between Taft’s substitution constants and the wave numbers of the maxima of the absorption spectra of these complexes in the solid state is not clear.
Studies on Cobaloxime Compounds. II. Catalytic Activity of Cobaloximes in the Hydrogen Peroxide Decomposition Reaction
Authors: Hohokabe Yorikatsu , Yamazaki Noboru
Published: July 2006

Various cobaloximes with the general formula [CoX(DH)2B] (X: Cl, CN, OH, or CH3. DH: Dimethylglyoximato monoanion. B: Bases such as water, nicotinamide, pyridine, imidazole, or a low molecular weight copolymer of acrylamide and 4-vinylpyridine, etc.) were examined for catalytic activity in the H2O2 decomposition reaction. Cyanocobaloximes have less activities than other cobaloximes. The effect of changing the axial bases of cobaloximes was found to be small. When methylcobaloxime was used as a catalyst, the lag time was observed in the dark, while with the irradiation of visible light the reaction proceeded without induction period. An extensive study on chloroaquocobaloxime revealed that the rate is proportional both to the concentration of H2O2 and to the concentration of cobaloxime and inversely proportional to [H+]. It was found that the decomposition of H2O2 with cobaloximes proceeds with a gradual and partial degradation of cobaloximes.
γ-Induced Addition of Trialkyltin Hydrides to Unsaturated Esters
Authors: Tsurugi Jitsuo , Iida Masaru , Nakao Ren , Fukumoto Tsugio , Murata Niro
Published: July 2006

γ-Induced hydrostannation of ethyl acrylate, allyl acetate, and vinyl acetate with triethyltin and tri-n-butyltin hydrides was attempted. The hydrostannation of ethyl acrylate and allyl acetate gave the corresponding adducts in almost quantitative yield. (2-Acetoxyethyl)-tri-n-butyltin expected from hydrostannation of vinyl acetate with tri-n-butyltin hydride could not be isolated. However, NMR and IR spectra indicated the formation of the adduct, which was found to decompose into ethylene and tri-n-butyltin acetate. The decomposition of the adduct was discussed in comparison with other adducts.
Biogenesis of the Essential Oils in Camphor Trees. XXVIII. On the Components of the Essential Oil of Cinnamomum japonicum Sieb.
Authors: Fujita Yasuji , Fujita Shin-ichi , Yoshikawa Hisashi
Published: July 2006

Cinnamomum japonicum Sieb. is sometimes divided into several varieties on the basis of morphological differences in the leaves. The essential oils of samples of this plant from various parts in Japan were examined from the viewpoint of chemotaxonomy. The results obtained from the materials gathered at Mt. Satsuki, Ikeda-shi, Osaka Prefecture, will be reported here first. The characteristics of the oil of the leaves and branchlets are the abundant presence of 1,8-cineole and p-cymene. The rich existence of linalool in the branchlet oil may also be a characteristic of this plant.
Studies on Cobaloxime Compounds. III. Effects of Various Cobaloximes as Vitamin B12 Models and of Substrate Analogs on Diol Dehydratase System
Authors: Hohokabe Yorikatsu , Yamazaki Noboru
Published: July 2006

Various types of cobaloximes with the general formula [CoX(DH)2B] or [RCo(DH)2B] (X: CI, CN. R: alkyl groups such as methyl, ethyl, n-propyl, or i-propyl. DH: dimethylglyoximato monoanion. B: bases such as water, pyridine, nicotinamide, γ-picoline, p-toluidine, or imidazole) and some amide compounds were examined for the inhibitory effect or coenzyme activity in propanediol dehydratase of Aerobacter aerogenes. None of them act as coenzyme nor inhibitor, except for cyanoaquocobaloxime, which shows only a weak inhibitory effect that has been proved to be non-competitive. Water-soluble polymeric cobaloximes with the general formula [Co(OH) (DH)2(Copoly–AM-VPy)] (Copoly–AM-VPy: a low molecular weight copolymer of acrylamide and 4-vinylpyridine) were also prepared and examined in the enzymatic system whose inhibitory effects were very small. Other cobaloximes with the general formula [RCo(DH)2(py)] (R: β-hydroxy-n-propyl, β-hydroxy-i-propyl, or β,γ-dihydroxy-n-propyl. py: pyridine) which were three of the possible intermediate models in propanediol dehydratase system, also showed little effect on the enzymatic reaction. Substrate anologs such as 2-bromo-1-propanol, 1-bromo-2-propanol, and glycerol α-monochlorohydrin, which are considered to interact with a nucleophilic Co(I) species, presumably a component of the active site in the holoenzyme, were found to serve as substrate.
The Reaction of α-Carbonyl Sulfides with Bases. II. The Effect of Variation in the Nucleophiles
Authors: Oki Michinori , Funakoshi Wataru
Published: July 2006

The reactions of α-alkylthio ketones with various nucleophiles were examined. It was found that such “strong bases” as ethoxide did not cause any cleavage of the C–S bond, whereas such “weak bases” as thiourea could cause the cleavage. The phenomena may be explained by the concept of soft-and-hard acids and bases. Discussions are given of some reactions of the nucleophilic attack on sulfur, which have previously been reported, in the light of this new reaction.
Group Interactions in Polyelectrolytes. V. The Kinetics of the Amination of Chloromethylated Polystyrene with 2-Aminobutanol
Authors: Kawabe Hiroshi , Yanagita Masaya
Published: July 2006

The amination of chloromethylated polystyrene with 2-aminobutanol in dioxane was studied. The apparent rate constatns, kapp, as computed by the simple second-order equation, were found to increase linearly with the degree of amination; this was in contrast with the amination with n-butylamine, in which the kapp decreased as the amination proceeded. By assuming that the reactivity of the chloromethyl group is enhanced when it is situated next to the already-aminated group as a result of the “hydrophilic effect” of the hydroxyl group, rate equations which give the elementary rate constants were derived. In the presence of a large excess of amine, the over-all kinetics can be expressed by:

dx⁄dt=[ab⁄(3k1−k2)][3k1(k1−k2)e−3k1at+2k1k2e−k2at]

where x is the concentration of chloride ions at time t; where a is the initial concentration of amine, and b, that of the chloromethyl group, and where k1 and k2 are the rate constants of the elementary reactions which are independent of the neighboring group and under the influence of it respectively. The values of kapp calculated on the basis of k1 and k2 were also found to agree with the observed values.
Electronic Spectra and Electrical Resistivities of the Molecular Complexes of Benzidine and Its Derivatives
Authors: Matsunaga Yoshio , Saito Gunzi
Published: July 2006

The electronic structures of about sixty polycrystalline molecular complexes of benzidine and its derivatives have been examined on the basis of the vibrational and electronic spectra. The complexes show a strong tendency to be non-ionic, in spite of the low ionization potentials of the electron donors. Several non-ionic complexes exhibiting resistivities of the order of 103–105 ohm cm have been found. The optical and electrical properties of the complexes consisting of donor molecules with amino groups and of acceptor molecules with carbonyl groups are distinctly different from those of the others. The first charge-transfer absorption band of the solid complex in the former group appears at an energy considerably lower than that of the corresponding complex in chloroform. Moreover, the activation energy for semiconduction seems to be appreciably reduced by the formation of a hydrogen bond.
Preparation and Properties of N,N-Dialkylethylenediamine N-Oxide Complexes of Nickel(II), Copper(II), and Cobalt(III)
Authors: Kida Sigeo , Oniki Takayuki
Published: July 2006

The complexes of Ni(II), Cu(II), and Co(III) with N,N-Dialkylethylenediamine (alkyl=CH3, C2H5, and C3H7) have been prepared. It was revealed that these ligands coordinate to metal ions as bidentate ligands with amino and tertiary amine oxide groups. Two forms have been obtained for the 1 : 2 nickel(II) complexes, the hydrated green form with μeff=3.3 and the anhydrous red or reddish brown form with zero or very low magnetic moment. They are easily convertible into each other. Formation of square planar diamagnetic Ni(II) complexes with ionic-type ligand was interpreted in terms of the steric effect of the alkyl groups.
The Synthesis and Properties of trans-[CrCl2(NH3)4]Cl·H2O
Authors: Nagase Kenzo , Tanaka Nobuyuki
Published: July 2006

A simple method for the synthesis of trans-dichlorotetraamminechromium(III) chloride monohydrate was developed, and the configuration of the complex obtained was confirmed by measurements of the infrared and visible absorption spectra. It was found that the cis-trans isomerization took place in the solid state upon the thermal treatment of the complex at 200°C. The enthalpy change for the reaction was calculated to be 1.2 kcal·mol−1 by an analysis of the DSC curve.
The Photochemical Decomposition of Ethylamine as Studied by Means of the Electron Spin Resonance
Authors: Kotake Yashige , Ono Mitsuo , Kuwata Keiji
Published: July 2006

The photochemical decomposition of ethylamine at low temperatures was studied using ultra-violet light of various wavelengths (120–400 nm), and the photochemical reactions were examined. The initial stage of the decomposition is the release of the hydrogen atom by far ultra-violet light. As the decomposition proceeds, the effective wavelengths for the succeeding reactions become longer. The final products of the decomposition are the methyl radical and other diamagnetic species. The effects of the matrix and the counter ion on the reaction are also discussed.
Thermochromisms of Some β-Diketone Chelate Copmlexes of Copper(II) in Pure Pyridine
Authors: Yokoi Hiroshi , Sai Mitsuru , Isobe Taro
Published: July 2006

Two types of thermochromisms have been found for several β-diketone chelate complexes of copper(II) in pure pyridine or γ-picoline. One is observed for such complexes as bis(acetylacetonato)copper(II). In this case, the visible absorption spectra at various temperatures have well-defined isosbestic points; there are two different complex species, L and H, at equilibrium in the solvent, where L and H represent the low-temperature and high-temperature species respectively; they are different in the interaction between the complex and pyridine or γ-picoline molecules. The other is observed for such complexes as bis(salicylaldehydato)copper(II), where the spectral intensity increases remarkably with a rise in the temperature. The equilibrium for bis(acetylacetonato)copper(II) was studied over the temperature range of 0–60°C, and the results were used to derive the approximate thermodynamic parameters, ΔH=4.0±1.0 kcal/mol and ΔS=13±4 e.u., for the L→H change. The most probable structures for L and H were suggested from a spectrophotometrical point of view.
The Photochemical Degradation of Diphenyl Sulfone-1-14C
Authors: Nakai Mamoru , Furukawa Naomichi , Oae Shigeru , Nakabayashi Takeshige
Published: July 2006

The photolysis of diphenyl sulfone-1-14C upon irradiation with 2537 Å light in benzene gave biphenyl-1-14C and benzenesulfinic acid-14C. The yields of both compounds were estimated by means of an isotope dilution method. The 14C activity of the sulfone recovered was equal to that of the sulfone employed, while that of biphenyl formed was found to have nearly one half of the 14C activity. These results reveal that the phenylation reaction by phenyl radical formed by the photolytic cleavage of the C–S bond of the sulfone is an intermolecular reaction in which benzenesulfonyl radical appears to abstract hydrogen from the intermediate cyclohexadienyl radical rather than attacking benzene. The 14C distribution indicates that the 14C activity at 1-position was found to remain at the same position of biphenyl after photolysis of the sulfone. Thus, the photolysis of diaryl sulfones in benzene followed by the oxidation of biphenyl derivatives obtained would be a convenient method for the degradation of diaryl sulfones.
Synthesis and Conformation of Cyclopropane Intermediates in the Total Synthesis of Illudin M and S
Authors: Matsumoto Takeshi , Shirahama Haruhisa , Ichihara Akitami , Shin Hyonsobb , Kagawa Shohei , Hisamitsu Toshiaki , Kamada Toshihiro , Sakan Fujio
Published: July 2006

Several promising cyclopropane intermediates in the total synthesis of illudin M and S have been prepared. Survey of NMR of these compounds showed the conformation 17 to be unfavourable.
Acylation of Nδ-Benzyloxyornithine
Authors: Isowa Yoshikazu , Takashima Toshiyuki , Ohmori Muneki , Kurita Hideaki , Sato Masanari , Mori Kaoru
Published: July 2006

Acetylation of Nδ-benzyloxyornithine monohydrobromide (I·HBr) with acetic anhydride gave the Nδ-acetylated product, which yielded Nδ-acetyl-Nδ-hydroxyornithine by catalytic reduction. On the other hand, acetylation or alkoxycarbonylation of Nδ-benzyloxyornithine(I) proceeded through Nα-acetylation, followed by spontaneous cyclization to form lactams, which yielded cyclic hydroxamic acids on catalytic reduction. These hydroxamic acid and Nδ-acetyl-Nδ-hydroxyornithine were readily hydrolyzed to give Nδ-hydroxyornithine.
Synthesis of Rhodotorulic Acid
Authors: Isowa Yoshikazu , Takashima Toshiyuki , Ohmori Muneki , Kurita Hideaki , Sato Masanari , Mori Kaoru
Published: July 2006

Rhodotorulic acid (I) was synthesized by a series of reaction starting from Nδ-tosyl-Nδ-benzyloxy-l-ornithine. Detosylation and acetylation of intermediate, cyclo-di-Nδ-tosyl-Nδ-benzyloxy-l-ornithyl (Ll-IX), afforded cyclo-di-Nδ-acetyl-Nδ-benzyloxy-l-ornithyl (Ll-XI), which, on reductive debenzylation, gave rhodotorulic acid.
Studies of Acyl and Thioacyl Isocyanates. VIII. Cycloaddition Reactions of Benzoyl and Thiobenzoyl Isocyanates with Carbodiimides
Authors: Tsuge Otohiko , Sakai Kazuko
Published: July 2006

The investigations of cycloaddition reactions of benzoyl and thiobenzoyl isocyanates with carbodiimides have shown that the adducts formed from benzoyl isocyanates and N,N′-dicyclohexylcarbodiimide are the corresponding (4+2) cycloadducts, and not the (2+2) cycloadducts proposed by Neidlein. The reaction of isocyanates with N,N′-diphenylcarbodiimide at 0°C gave (2+2) cycloadducts, which were thermally isomerized into the corresponding (4+2) cycloadducts. Benzoyl isocyanates reacted with N-cyclohexyl-N′-phenylcarbodiimide to give (4+2) cycloadducts of isocyanates to the cyclohexyl-N=C bond in the carbodiimide. On treatment with neutral alumina, (4+2) cycloadducts were easily isomerized into 1,3,5-triazines. Thiobenzoyl isocyanate reacted with both the N=C bonds of the carbodiimide to afford two isomeric (4+2) cycloadducts. It has been found that benzoyl isocyanates reacted with N-phenyl-N′-o-tolylcarbodiimide to yield the corresponding (4+2) cycloadducts of isocyanates to the o-tolyl-N=C bond and/or the isomeric 1,3,5-oxadiazin-6-ones, depending on the nature of the substituent in the isocyanate. Reaction paths for the formation of the product are also discussed.
An Interstitial-Electron Model for the Structure of Metals and Alloys II. Electronic Structure of Metals of Groups I–V
Authors: Johnson Oliver
Published: July 2006

The interstitial-electron model leads to metal structures which are instantaneous pictures of electron distribution written in terms of metal ion core charge Mn+ (n=valency) and numbers of electrons in octahedral or tetrahedral interstices. On the average there are \bare in all interstices, and the degree of electron localization is small in metals. Decisions as to electron occupancy of interstices are primarily based on considerations of \bare spin and of screening of \bare by ion cores, but electronic heat capacity, Hall coefficient and anisotropy in magnetic susceptibility are of use in making decisions on electron occupancy of interstices. For univalent metals there is little localization of \bare because of the large excess of vacant interstices. This is also true when interstices approach full occupancy by (\bare)2 as in M4+ and M5+. Among divalent and trivalent metals the preferential occupancy of interstices leads to considerable localization of \bare density for Be, Sc, Y, and Tl. This high degree of localization is a consequence of mutual polarization of ion cores and \bare; it accounts for the lattice distortion in these metals and leads to other unusual properties.
Spectral Shift of Band Origins in the Near Ultraviolet Absorption Spectra of Some 2- and 3-Substituted Pyridines
Authors: Kastha G S , Bag S C
Published: July 2006

The relative shifts in the position of band origin of the lowest singlet π-electron transition in some 2- and 3-substituted pyridines, and monosubstituted benzenes with similar substituents, with respect to those of the parent molecules have been calculated by the method of localized orbitals with configuration interaction. Under certain assumptions, the calculated relative shifts in the 2- and 3-substituted pyridines are found to bear a linear relationship with that of the corresponding monosubstituted benzenes. The experimental data are found to be in agreement with the theoretical expectation.
Polarography of Uranyl Complex with p-Aminothiophenoxyacetic Acid in Dimethyl Sulfoxide Solution
Authors: Lai Tsai-Teh , Yang Jan-Chin
Published: July 2006

The polarography of uranyl ion in dimethyl sulfoxide (DMSO) was investigated in the DMSO concentration range 40–99 vol%. The complex species identified is UO2(DMSO)62+; it is transformed into UO2(DMSO)2+ and UO2+ after the electrode reduction. In the presence of p-aminothiophenoxyacetic acid, the uranyl ion in the DMSO medium produces a two-step wave at lower pH and higher concentration of DMSO. The limiting current of the wave is controlled partially by the kinetics of the preceding chemical reaction and partially by the diffusion of the complex. The rate constant and diffusion coefficient of the reduction process were determined. At pH around 4, the formation of binuclear uranyl complexes was confirmed.
Distribution Studies of the Potassium Salts with Hexanitrodiphenylamine and Analogous Acids
Authors: Iwachido Tadashi
Published: July 2006

The association constants of potassium salts with 2,4,6,2′,4′,6′-hexanitrodiphenylamine (hexyl), N-(2,4,6-trinitrobenzo)-2,4-dinitro-l-naphthylamine (α-hexyl), and l,3,7,9-tetranitrophenothiazine-5-oxide (thiohexyl) in the nitrobenzene phase were determined conductometrically. The distribution constants and the association constants of these salts in an aqueous phase were determined simultaneously by means of solvent extraction. The dissociation constants in the aqueous phase and the distribution constants of the acids were estimated from an analysis of the curve obtained by plotting the distribution ratios of the metal or the acids against the pH. The results show that these salts exist mainly in the dissociated form in both phases. The applicability of the proposed distribution mechanism was also discussed.
Kinetic Studies of the Nickel Malate Complex Formation in Solution by the Pressure-jump Method
Authors: Harada Shoji , Amidaiji Katsuyoshi , Yasunaga Tatsuya
Published: July 2006

The nickel malate complex formation reaction in an aqueous solution, Ni2++Mal2−\oversetkf\undersetkd\ightleftharpoonsNiMal, where Mal2− represents the malate ion, was studied by the pressure-jump method. The following rate constants and the equilibrium constant were obtained: kf=5.6×105  m−1 sec−1, kd=17 sec−1 and K=3×104  m−1 at 25°C and μ→0. Studies at various temperatures between 12 and 30.5°C gave the thermodynamic parameters. In comparison with the results on other ligand complexes, the ligand effects seem to be found not in the formation rate constant, but in the dissociation rate constant. The results indicate that the rate-determining step of the complex formation is the release of the water molecule from the inner coordination sphere of the nickel ion.
Studies on Stable Free Radicals. X. Photolysis of Hindered N-Chloroamines
Authors: Toda Toshimasa , Mori Eiko , Horiuchi Hideo , Murayama Keisuke
Published: July 2006

Photolysis of the hindered N-Chloroamines, 1-chloro-2,2,6,6-tetramethyl-4-oxopiperidine (IIa), 1-chloro-2,2,6,6-tetramethylpiperidine (IIb), and 1-chloro-2,2,5,5-tetramethyl-4-oxoimidazolidine (IIc), in benzene solution were carried out in an ESR spectrometer cavity. The ESR spectra of the corresponding amino radicals IIIa, IIIb, and IIIc were observed in evacuated solutions. In solutions containing oxygen, it was found that amino radicals IIIb and IIIc, readily reacted with oxygen to give the corresponding stable nitroxide radicals IVb and IVc, from the shapes of spectra and g-values. Amino radical IIIa did not react with oxygen. Although the amino radicals could not be isolated, their formation was confirmed by the isolation of a coupling product with a benzyl radical generated from dibenzylmercury.
Mechanism of Hydrogen Exchange Reactions on 1:2 Electron Donor-Acceptor Complexes of Anthracene with Sodium
Authors: Ichikawa Masaru , Tanaka Sadao , Naito Shuichi , Nakamura Takahiro , Soma Mitsuyuki , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The mechanisms of the H2–D2 and D2–HZ exchange reactions over 1 : 2 Electron Donor-Acceptor (EDA) complexes of anthracene with sodium, where HZ denotes the EDA complexes, were studied kinetically and spectroscopically in the temperature range 20–90°C. It was found that molecular hydrogen exchanges directly with the hydrogen of the complexes (An2−2Na+ or An−Na+) and also with the monohydroanion complex (AnH−Na+), which is formed by the dissociative adsorption of hydrogen. The H2–D2 exchange reaction proceeded via not only the σ-bonded hydrogen of the complexes, but also homolytically dissociated “mobile” hydrogen.
Ion-Solvent Interaction of Tetraalkylammonium Ions in Solvents of High Dielectric Constant. II. Conductance and Walden Product of Tetraalkylammonium Ions in N-Methylformamide and N-Methylpropionamide at Different Temperatures
Authors: Singh Raj Deo , Gopal Ram
Published: July 2006

Ion-solvent interaction of the tetraalkylammonium ions (R4N+) in N-methylformamide and N-methylpropionamide has been investigated from the electrical conductance point of view. It appears that the R4N+ ions act as net structure breakers in these solvents as in N-methylacetamide. The appreciable negative deviation of the experimental slope of the Λ vs. \sqrtc curves from the theoretical slope suggests some kind of obstruction to the movement of the R4N+ ions, probably due to their unwieldy size or to some kind of cation-anion association, although the usual kind of association is ruled out in view of the high dielectric constant of these solvents. The cation-anion interaction may be the penetration of the cations by the anions which has been suggested as a possible reason for the negative slope in the apparent molal volume vs. \sqrtc curves, obtained at higher concentrations, to which apparent molal volume measurements usually have to be confined on account of difficulties in accurate density measurements at low concentrations. The smaller alkali metal ions appear to be more solvated than the R4N+ ions, so much so that the λ0+-values of Na+ and K+ ions are lower than the corresponding values of the Me4N+ and Et4N+ ions.
Study of Hydration and Association of Ions in Solution. II. Complete Resolution of Tris(ethylenediamine)Cobalt(III), Chromium(III), and Rhodium(III) Complexes by Means of Paper Electrophoresis
Authors: Yoneda Hayami , Miura Takao
Published: July 2006

Complete resolution of racemic [M en3]3+ (M=CoIII, CrIII, and RhIII) by means of electrophoresis was achieved in a background solution of sodium d-tartrate and aluminum chloride. Electrophoretic data obtained under various conditions (various compositions, concentrations, and pH values of supporting electrolyte solutions) indicated that the separation of the enantiomers of [M en3]3+ complexes was accomplished not by the d-tartrate anion but by some aluminum d-tartrate complex anion.
Metal Complexes Containing Six-Membered Chelate Rings. II. Preparation and Structure of 2,4-Pentanediamine Complexes of Cobalt(III)
Authors: Mizukami Fujio , Ito Haruko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

New cobalt(III) complexes containing optically active (RR and SS) and meso(RS) 2,4-pentanediamine (2,4-ptn) have been synthesized. [Co(RR-2,4-ptn)3]3+ gives two diastereoisomers, prismatic crystals with (−)546 rotation and needle-like crystals with (+)546 rotation. The former is produced much more than the latter. The conformations of the RR- (or SS-) and RS-2,4-pentanediamine chelate of the complexes were assigned to λ- (or δ-) twist and chair form, respectively, from comparison of their PMR spectra with those of the corresponding tetra-acetato complexes. [Co(RS-2,4-ptn)3]3+ seems to have fac structure with respect to the coordination of the amino groups adjacent to the R- and S-carbon atoms. The circular dichroism spectra of mono and trans-bis-(RR-2,4-ptn) complexes in the first band region are essentially the same as those of the corresponding R-propylenediamine complexes. The circular dichroism spectra of (+)546- and (−)546-[Co(RR-2,4-ptn)3]3+ and (−)546-[Co(RS-2,4-ptn)3]3+ are very different from those of the triscobalt(III) complexes of R-propylenediamine and trimethylenediamine. Such differences have been discussed with reference to the stereochemistry of six-membered chelate complexes.
ESR Studies of the Copper(II) Complexes of Ammo Acids
Authors: Yokoi Hiroshi , Sai Mitsuru , Isobe Taro , Ohsawa Shigeru
Published: July 2006

The X-band and K-band ESR spectra of the trans-planar copper(II) complexes of amino acids, whose crystal structures are now known, were measured in a polycrystalline state at room temperature and in frozen aqueous-methanolic solutions at the temperature of liquid nitrogen. The polycrystalline samples showed a variety of ESR line shapes, most of which had three different principal g values; g1=2.04–2.07, g2=2.08–2.12, and g3=2.16–2.29. On the other hand, all the ESR line shapes observed for the frozen solutions were quite similar, and they indicate a normal tetragonal copper (II)-ion environment. There was, moreover, a remarkable difference in the g values between the complexes in the two states. The correlation among the g values, the d-d band energies, the bonding parameters (a measure of the degree of covalency of the copper-ligand bondings), and the geometrical configurations of the coordinating atoms for the complexes in a crystal is discussed in some detail.
The Photo-induced Electron Transfer Reactions between Crystals of Aromatic Hydrocarbons and Quinones
Authors: Soma Mitsuyuki
Published: July 2006

The photo-induced electron transfer reactions between crystals of aromatic hydrocarbons and several quinones were studied by measuring the increase of the photocurrent in the crystals due to the carrier injection from the ethanol electrode containing the quinones. The reaction rates were shown to be independent of sorts of quinones used when its concentration was sufficiently high. The excitation limited mechanism of the reaction was proposed to be consistent with this behavior and the observed concentration dependence of the reaction.
Isotopic Exchange Kinetics between Trisacetylacetonatocobalt(III) and Acetylacetone-14C in Organic Solvents
Authors: Saito Kazuo , Murakami Mizue
Published: July 2006

The isotopic exchange proceeds faster than the decomposition of the complex at more than 80°C and below 120°C. McKay plot gives a linear diagram at the initial stage of isotopic exchange. The rate is expressed by R=[complex](k1+k2[acacH]), where acacH stands for free acetylacetone. The Arrhenius activation energy decreases in the order anisole (25 kcal per mole), chlorobenzene (21), and toluene (18) and is subject to acid catalysis with a strong acid as trichloroacetic. Comparison of the data with those of racemization of this complex, and isomerization and inversion of tris(benzoylacetonato)cobalt(III) suggested that k1 represents dissociation mechanism through a five coordinate intermediate containing a unidentate acetylacetonate anion, and the k2 an association mechanism involving association of free acacH with the intermediate.
Peptides Containing Aminophosphonic Acids. I. Reactivity of α-Aminobenzylphosphonic Acid
Authors: Yamauchi Kiyoshi , Kinoshita Masayoshi , Imoto Minoru
Published: July 2006

The chemical reactivity of α-aminobenzylphosphonic acid was investigated in order to survey the methods for incorporating aminophosphonic acids into a peptide chain. The investigation revealed that i) a dipeptide analog linked with a phosphonamide bond could be produced by the reaction of C-protected amino acid with the N-protected aminophosphonomonochloridate, and that ii) amino groups of the aminophosphonic acid possessed a reactivity similar to those of amino acids, and were capable of coupling with N-protected amino acids by means of dicyclohexylcarbodiimide.
A Kinetic Study of the Polymerization of Acrylic Acid in the Presence of Polyvinylpyrrolidone
Authors: Muramatsu Ryo , Shimidzu Takeo
Published: July 2006

The polymerization of acrylic acid (AA) in a dilute aqueous solution in the presence of polyvinylpyrrolidone (PVP) has been studied kinetically, with the extent of polymerization followed by a bromometric titration method. The rate of the polymerization changed characteristically with the amount of PVP in the solution and went through a maximum at a certain initial mole ratio of PVP and AA, [PVP]0/[AA]0, under a constant [AA]0 value. The mole ratio which gave the maximum rate was almost proportional to the reciprocal of [AA]0. In the course of the polymerization, a polymer complex consisting of PVP and polymerized AA was precipitated. Its composition, (PAA)c/(PVP)c, has been found to be different as the polymerization conditions are varied. Hardly no comparable data between the bromometric method and a turbidimetric method used to measure the rate were obtained. The influence of PVP on the polymerization was assumed to be caused by the local concentration of AA in the vicinity of PVP. A mechanism based on the effect of the local concentration, the “polymer atmosphere binding mechanism,” has been found to explain the experimental results well.