bluuebunny/crossref_metadata_2025 huggingface dataset:
Interaction between Excited β-Naphthol and Pyridine. Hydrogenbond Formation in S* and H-Transfer Reaction in T
Authors: Kikuchi Koichi , Watarai Hitoshi , Koizumi Masao
Published: July 2006

The interaction between the excited β-naphthol and pyridine in cyclohexane has been investigated by an absorption-emission flash technique. The triplet naphthol has been found to be deactivated by pyridine with the rate constant of 1.5–1.9×109 M−1sec−1, yielding naphthoxyl radical. With 10−4 M pyridine the triplet naphthol is completely transformed into naphthoxyl radical. Above 10−1 M pyridine naphthol exists almost exclusively as a H-bonded species in the ground state, which is non-fluorescent and produces no transient species detectable by an ordinary flash apparatus. For 10−4–10−1 M pyridine, the singlet excited naphthol undergoes collisional deactivation which most likely leads to a H-bonded species (rate constant, 1.2–1.4×1010 M−1sec−1). At the same time naphthoxyl radical is also produced with about the same rate constant as that for the triplet state. The results strongly suggest that the mechanism for the internal conversion of the singlet excited state via H-bonding is a transient H-atom transfer.
The Enthalpies of Binary Mixtures of Chalcogen Elements
Authors: Maekawa Takashi , Yokokawa Toshio , Niwa Kichizo
Published: July 2006

The enthalpies of binary mixtures among chalcogen elements were measured by means of calorimetry. In the system of sulfur+selenium, the positive enthalpy increment suggests the formation of a co-ring and a co-chain on mixing. In the selenium+tellurium and sulfur+tellurium systems, some local ordered structures were deduced from the minimum points of the enthalpy at the compositions of Te3Se2 and Te3S. In the latter system, the entropy of mixing was calculated from the reported phase diagram and the present enthalpy values. The entropy diagram also suggests that the local order is present.
The Reflection Spectra of Würster’s Salts
Authors: Oohashi Yukako , Sakata Tadayoshi
Published: July 2006

The reflections of N,N-dimethyl-p-phenylenediamine (WR) perchlorate, bromide, and iodide, and also of p-phenylenediamine (PD) perchlorate and bromide were measured over the range from 5000 to 42000 cm−1 by Avery’s method. The absolute absorption intensity and the refractive index of these solids were obtained by computer analysis. The absorption intensity of the solid was found to be, as a whole, larger than that of the dimer in solution; in particular, the CT band becomes broader and splits in a solid. Further, the anion was found to have a large effect on the electronic structure in the crystal. By taking account of these features of the spectrum and other experimental results, the WR salts were classified into two types according to their way of packing: Type I takes the dimer-unit structure (WRP) and Type II, the equidistantly-overlapped form (WRB and WRI).
The Preparation and Crystal Structure of Ternary Rare Earth Borides, RCo3B2
Authors: Niihara Koichi , Yajima Seishi
Published: July 2006

In the ternary system of rare earth-cobalt-boron, RCo3B2 compounds (R=rare earth elements) were prepared by arc-melting methods. Their crystal structure was investigated by X-ray diffraction methods. These ternary borides, RCo3B2, crystallize in a hexagonal lattice. The lattice parameters are a=5.020±0.002 Å and c=3.027±0.002 Å for YCo3B2 and a=5.066±0.003 Å and c=3.022±0.002 Å for GdCo3B2. The good agreement between the X-ray diffraction intensities observed and calculated shows that the ternary borides, YCo3B2 and GdCo3B2, crystallize in the CaZn5-type structure. The space group and atomic positions are as follows: P6/mmm (D6h1), 1R in 1(a), 3Co in 3(g), and 2B in 2(c). It can be seen from these results that the ternary borides, RCo3B2, have a superstructure in which two Co atoms in the 2(c) site of intermetallic compounds, RCo5, with the CaZn5-type structure are replaced by two B atoms. The B atoms in this structure are situated at the center of a trigonal prism formed by six Co atoms. The interatomic distances between B and the six Co atoms are 2.11–2.10 Å and are fairly constant, although the radii of the rare earth atoms are changed according to the lanthanide con-traction. We have also found RCo3B2 compounds to be isostructural with YCo3B2 and GdCo3B2, where R=Ce, Sm, Tb, Dy, Ho, and Er. Efforts to prepare LaCo3B2, PrCo3B2, and NdCo3B2 by arc-melting were unsuccessful.
Theoretical Calculations and Assignments of Electronic Absorption Spectra of Cation Radicals of o-, m-, and p-Disubstituted Benzenes Having Amino and Hydroxyl Groups
Authors: Katsumata Shunji , Kimura Katsumi
Published: July 2006

Calculations have been carried out on the electronic spectra and electronic structures of the cation radicals of o-, m-, and p-disubstituted benzenes having the amino and hydroxyl groups, by an open shell SCF MO CI method involving some doubly excited electron configurations. Assignments of the electronic absorption spectra of these cation radicals have been made on the basis of resulting transition energies and oscillator strengths. The results are in good agreement with experimental data. Effects of methyl-substitution on the cation spectra are discussed. Spin densities of these cation radicals have also been calculated and compared with experimental data.
The Magnetic Properties of Some Iminoxyl Polyradicals. IV. The Paramagnetic Susceptibilities of the Diluted Crystals of the TEMPAD Biradical
Authors: Nakajima Akira
Published: July 2006

The paramagnetic susceptibilities of the diluted crystals of bis (2,2,6,6-tetramethylpiperidine-4)azine-1,1′-dioxyl (the TEMPAD biradical) have been measured from 1.8 to 77.3 K. The χM-T curves obey the Curie-Weiss law in the high and low temperature regions, and two kinds of the Weiss constant were found. The Weiss constant in the high-temperature region, which is caused by the strong inter-molecular exchange interaction, varies with the radical concentration from −8.5 to −15 K. The Weiss constant in the low-temperature region is of the order of magnitude of −1 K and reveals the existence of a weak intra-molecular exchange interaction. We can assume that the TEMPAD biradicals are distributed randomly in the matrix of the diamine and that they form either an isolated portion in which the weak intra-molecular exchange interaction exists only, or a clustering portion coupled by a strong inter-molecular exchange interaction besides the intra-molecular one. Then, the concentration dependence of the χM-T curves can be explained as the superposition of the contributions from these two portions. The curves caluclated on the assumption of the random distribution agreed with the experimental results.
The Dependence of the Electron-transfer Rates of Aromatic Hydrocarbon Anion Radicals upon the Molecular Radii of the Reactants
Authors: Suga Kosaku , Ishikawa Shin-ichi , Aoyagui Shigeru
Published: July 2006

The applicability of the theory of R. A. Marcus is tested, the behavior of the rate constant being examined as a function of the molecular radii of the reactants. The rate constants of the electron-transfer reactions from the anion radicals of pyrene, perylene, and tetracene to their respective parent molecules are measured under experimental conditions in which the anion radicals are in a free ion or loose ion-pair state. The rate constants thus obtained and subsequently corrected for diffusion are 2.8×109, 3.0×109, and 2.6×109 M−1sec−1 respectively, in 1,2-dimethoxyethane at 25°C. These rate constants, as well as others obtained elsewhere for naphthalene and anthracene, are compared with those predicted theoretically, assuming a spherical and an oblate spheroidal molecular shape. The consistence between the theoretical and experimental results is not satisfactory; the variation in the observed rate constants with the molecular radii of the reactants is much smaller than that expected theoretically. The spin-exchange rate constants for anion radicals of pyrene, perylene, and tetracene are also determined to be 7.0×109, 5.1×109, and 4.8×109 M−1sec−1 respectively, in the same solvent at 25°C.
Isothermal Decay of Trapped Electron in Irradiated 2-Methyltetrahydrofuran Glass
Authors: Ichikawa Tsuneki , Yoshida Hiroshi , Hayashi Koichiro
Published: July 2006

The isothermal decay of the electron trapped in gamma-irradiated 2-methyltetrahydrofuran glass was studied by electron spin resonance measurements at 92–95 K. Shape of the decay curves was found to be independent not only of radiation dose but also of temperature if they were plotted on the time scale in unit of half-life at each temperature studied. Although the decay follows neither a first order nor a second order reaction, the activation energy is able to be determined uniquely to be 0.8 eV. These results indicate that the mobilization of trapped electron is caused by repeated sequences of detrap-retrap due to thermal distortion or destruction of traps and that the evolution of decay is determined by the initial distribution of the electron-cation separation. On the basis of Nernst-Einstein assumption, the normalized distribution of the separation distance is numerically obtained and found to be close to a Gaussian function, though the absolute value of distance is unable to be determined because of the lack of knowledge of diffusion coefficient for the migration of electron in the glass. The effect of partial photobleaching of the trapped electron on the isothermal decay for the rest of electron was also studied and found to be the same as that of partial thermal bleaching.
Kinetics and Mechanism of the Reaction of Iodine Mono Chloride with Some Alcohols
Authors: Das C R , Bose A N
Published: July 2006

Kinetics of the reaction of ICl with some aliphatic alcohols, methanol to n-butanol and isobutyl alcohol and isopropyl alcohol, have been studied by the conductance method at five different temperatures. Arrhenius parameters have been determined. Plot of log k against the reciprocal of dielectric constant has been drawn to test the applicability of the Amis and Jaffé equation. Energy of activation has been correlated with polarity of alcohols. The IR analysis of the product shows a sharp peak at 1620 cm−1, which confirms a (O–I) bond stretching in the product. From these results a reasonable mechanism has been suggested as follows:

ICl\xrightarrowfastI++Cl− (1)

R–O–H+I+\xrightarrowslowR–O–I+H+ (2)
The Photolysis of Cyclopentanone
Authors: Tsunashima Shigeru , Ohsawa Osamu , Takahashi Chiharu , Sato Shin
Published: July 2006

The 326.1 nm direct photolysis and the cadmium-photosensitized reactions of cyclopentanone have been compared in order to clarify the role of the triplet state of cyclopentanone in the photolysis. The products observed in the both photolyses were carbon monoxide, ethylene, cyclobutane, and 4-pentenal. The results obtained in the direct photolysis were very similar to those obtained in the cadmium photosensitization. The ethylene/cyclobutane ratio was not affected by the pressure and temperature changes. The 4-pentenal/CO ratio increased with a decrease in the temperature. These similarities suggest that the decomposition of cyclopentanone takes place through the lowest triplet state in both the photolyses. The efficiency of cyclopentanone in quenching triplet cadmium was found to be about 0.8 times that of cis-2-butene.
Synthesis and Metal Chelate Stability of N,N′-Ethylenebis(aminomalonic) Acid
Authors: Mashihara Misao , Ando Takeshi , Murase Ichiro
Published: July 2006

N,N′-Ethylenebis(aminomalonic) acid (EAMA) has been synthesized, and its acid dissociation constants and the stability constants of its alkaline earth metal complexes were determined potentiometrically at 25°C in a medium of ionic strength of 0.10 (KNO3) with the following results: pK1=2.1, pK2=2.72, pK3=6.56, pK4=9.69; logKMY and logMMHY for Ca(II) respectively, 5.45 and 2.02; for Mg(II) respectively 4.93 and 1.80. The exact stability constants of Cu(II) and Ni(II) chelates of this ligand were not obtained on account of its decomposition in low pH solution, but the order of relative stability has been established. From a comparison of the stability of Ca(II) and Mg(II) chelates with those of the analogous complexane, the function of the malonate group in the chelate formation has been discussed. Zn(II) and Co(II) chelates of this ligand have been obtained and their probable structures are proposed.
Detosylation of N-Tosyl Amino Acids and Peptides by Electrolytic Reduction
Authors: Iwasaki Tameo , Matsumoto Kazuo , Matsuoka Manabu , Takahashi Takeo , Okumura Kentaro
Published: July 2006

An electrolytic reductive cleavage of tosyl group in N-tosyl amino acids was carried out by the use of 2 mol equivalent of NaCl or KCl as an electrolyte to the tosyl amino acids and of lead as a cathode in methanol–water. The procedure was applicable to the cleavage of N-tosyl peptides with preservation of the peptide bond, and with retention of their optical activity. No cleavage of the other protecting groups such as urethane type group and benzyl group was observed. The optimum conditions for reductive cleavage were found to be pH 11, lead being preferable to other cathode metals.
Studies of Organo Sulfur Compounds. II. The Preparation and Reactions of Benzoyl Benzenethiosulfonates
Authors: Kato Shinzi , Mizuta Masateru
Published: July 2006

Some mixed sulfonic thiocarboxylic anhydrides (II, R, R′: Aryl) were obtained from the reactions of potassium substituted-thiobenzoate with benzene- or p-toluenesulfonyl chlorides. The reactions of benzoyl benzenethiosulfonate were examined in comparison with those of the corresponding mixed sulfonic carboxylic anhydrides.
Solvolysis of Organic Phosphates. VI. Intramolecular Catalysis in the Hydrolysis of 2-Pyridylalkyl Phosphates
Authors: Murakami Yukito , Sunamoto Junzo , Kanamoto Naomi
Published: July 2006

The spontaneous hydrolysis of 2-pyridylethyl, 2-pyridylpropyl, and 6-methyl-2-pyridylmethyl phosphates was investigated at 80–95°C in aqueous media with an ionic strength of 0.10. The reactions followed apparent first-order kinetics with respect to the phosphate species, and the maximum rates were observed at −log[H+] 2–3 with a shoulder around 5–6. The participation of intramolecular catalysis played by the pyridinium group in the hydrolysis of the above pyridylalkyl phosphates as well as in that of 2-pyridylmethyl phosphate was investigated from the LFER viewpoint. For the evaluation of LFER, the acid dissociation constant was employed as the most reasonable structural parameter. As a result, the intramolecular pyridinium catalysis was found to takes place in the zwitterion hydrolysis for 2-pyridylmethyl, 2-pyridylethyl, and 6-methyl-2-pyridylmethyl phosphates. This indicates the importance of the geometry around the reaction center for the intramolecular catalytic action. The isokinetic relationship was established for the hydrolysis of pyridylalkyl phosphates with the exception of 6-methyl-2-pyridylmethyl phosphate. The anomalous behavior in the hydrolysis of the latter was attributed to the activation entropy effect which may have been caused by defreezing of solvation in the transition state.
The Synthesis and Absolute Configuration of Optically Active Tricyclo[4.3.0.03,8]nonane (Twist-brendane)
Authors: Naemura Koichiro , Nakazaki Masao
Published: July 2006

(−)-Tricyclo[4.3.0.03,8]nonane (“twist-brendane”) was synthesized via (−)-tricyclo[4.3.0.03,8]nonan-2-one (“twist-brendan-2-one”). The absolute configuration, (1R,3S,6S,8R)-tricyclo[4.3.0.03,8]nonane was assigned to (−)-twist-brendane by correlating with (−)-endo-5-carboxybicyclo[2.2.1]heptane.
Cyclopropanes from Olefins by the Oxygen-accelerated Zinc-carbenoid Reaction
Authors: Miyano Sotaro , Hashimoto Harukichi
Published: July 2006

Oxygen greatly accelerates the cyclopropanation of olefins by the diethylzinc-chloroiodomethane or -diiodomethane system. Olefins, including cyclohexene, cyclooctene, 1-heptene, 1-octene, 2-heptene, indene, n-butyl vinyl ether, styrene, and methyl oleate, gave the corresponding cyclopropanes in yields of ca. 70–100%. The methylene addition to cis- and trans-2-butene proceeded in a stereospecific manner in the presence of oxygen. Methyl methacrylate gave no appreciable amount of cyclopropanated product, but polymerization proceeded. Styrene inhibited the formation of the zinc-carbenoid reagent from diethylzinc and dihalomethanes under a nitrogen atmosphere. AIBN and UV light initiated the cyclopropanation of styrene with diethylzinc and chloroiodomethane. A free-radical-chain mechanism is proposed for the formation of the zinc-carbenoid reagent from diethylzinc and dihalomethanes.
Catalytic Diacetoxylation of Dihaloethylenes in the Presence of Palladium Salts
Authors: Yamaji Masahiro , Fujiwara Yuzo , Asano Ryuzo , Teranishi Shiichiro
Published: July 2006

The reaction of dihaloethylenes with acetate anions in the presence of palladium(II) salts gave trans-diacetoxyethylenes catalytically. It was found that the system, PdCl2–NaOAc–CH3CN is the best for the diacetoxylation of dihaloethylenes, and that palladium(II) salts catalyze the isomerization of trans-diacetoxyethylene to its 1,1-diacetoxy derivative. The mechanism was also discussed.
Linear Conjugated Systems Bearing Aromatie Terminal Groups. XI. Syntheses and Electronic Spectra of α,ω-Diphenanthrylpolyenes
Authors: Takeuchi Yasuhira , Yasuhara Akio , Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

The syntheses of α,ω-di(2-phenanthryl)-, di(3-phenanthryl)-, and di(9-phenanthryl)polyenes (In, In′, and In″, n=1–6) by means of the Wittig reaction are described. Formylphenanthrenes (II, II′, II″), phenanthrylpropenals (III′, III″), phenanthrylpentadienals (IV, IV′, IV″) and muconaldehyde (VIII) were used as carbonyl components in the reaction. Phenanthrylmethyl-, phenanthrylpropenyl- and phenanthrylpentadienyltriphenylphosphonium bromides and l,4-bis(triphenylphosphonium)-2-butene dibromide were converted into phosphoranes (V, V′, V″, VI, VI′, VII″, IX, IX′, IX″, VII) by a reaction with phenyllithium. The reaction of carbonyl components with phosphoranes with a proper combination yielded diphenanthrylpolyenes (In, In′, In″). 2- and 3-Phenanthryl derivatives (In and In′) exhibited electronic spectra with well-defined vibartional fine structure, whereas 9-phenanthryl derivative (In″) showed broad and structureless absorption curves. It was found that the plots of the longest-wavelength maxima (λmax) of In and In′ against n0.6 and n0.8 give excellent straight lines which can be given by the empirical formulas:

In:λmax=57.9n0.6+303 nm (in tetrahydrofuran)

In′:λmax=30.3n0.8+348 nm (in tetrahydrofuran)
Kinetics and Mechanism of Aziridine Synthesis from Ketoxime with Lithium Aluminum Hydride
Authors: Tanida Hiroshi , Okada Tetsuo , Kotera Katsumi
Published: July 2006

The stoichiometry and rate of the reaction of dibenzyl ketoxime (1) with lithium aluminum hydride in tetrahydrofuran leading to cis-2-benzyl-3-phenylaziridine (2, 92%) and 2-amino-1,3-diphenylpropane (3, 8%) were determined by gas meter and vpc. It was found that the aziridine formation proceeds with an immediate evolution of 1 mole of hydrogen followed by a slow liberation of a second mole of hydrogen and an accommodation of 1 equiv. of hydride into the molecule. Also, the formation has an induction period and there is a catalytic acceleration effect by the concurrently-formed minor product 3. Combination of the previously-reported results and the present findings leads us to propose a mechanism by which an aluminum derivative rapidly obtained on addition of 1 to the solution of lithium aluminum hydride undergoes slow hydrogen elimination to afford an azirine intermediate, followed by reduction to the aziridine. Making use of the catalytic effect discovered, the reaction rate and yield of aziridine were increased by the addition to the reaction mixture of an amine, particularly a secondary amine such as n-butylmethylamine.
4-Epifriedelin and 4-Epishionone. Structure and Reflex Effect
Authors: Aoyagi Reiko , Yamada Sh\={u}z\={o} , Tsuyuki Takahiko , Takahashi Takeyoshi
Published: July 2006

4-Epifriedelin (III) and 4-epishionone (VII) were prepared by photoepimerization of friedelin (I) and shionone (VI), respectively. On base treatment, III and VII were completely isomerized into I and VI, respectively; this observation was discussed based on reflex effect.
Mesoionic 5-Acylimino-2-methylthiothiazoles
Authors: Shiba Toshie , Kato Hiroshi
Published: July 2006

Treatment of 5-acylamino-4-thiazoline-2-thiones (6) with methyl iodide followed by treatment with an alkali gave the corresponding mesoionic 5-acylimino-2-methylthiothiazoles (8) instead of the corresponding thiazolium salts. The reactions of 2-methylthiothiazoles (8) with nucleophiles gave 2-substituted 5-acylamino-4-thiazolines.
Synthesis of a Gramicidin S Analog Containing δ-Aminovaleric Acid, [4–5-δ-Aminovaleric Acid]-Gramicidin S
Authors: S\={o}fuku Sh\={o}suke
Published: July 2006

In order to investigate the contribution of amide bond in peptide to its activity and conformation, a new type of analog of gramicidin S, [4–δ-aminovaleric acid]-gramicidin S, was synthesized, in which one of the d-phenyl-alanyl-l-proline residues of gramicidin S was replaced with δ-aminovaleric acid residue. The analog peptide has antimicrobial activity and shows similar ORD and CD spectra to those of gramicidin S. The linear peptide (Val–Orn–Leu–δAva–Val–Orn–Leu–d–Phe–Pro) has no activity and its ORD and CD spectra are nearly the same as those of random coil of polypeptide.
The Syntheses of Heterocyclic Compounds by the Ternary Condensation of Malononitrile, Salicylaldehyde, and Aliphatic Ketones in the Presence of Ammonium Acetate
Authors: Sakurai Akio , Motomura Yoshito , Midorikawa Hiroshi
Published: July 2006

Various 2-amino-6-alkyl (or 5,6-dialkyl)-4-aryl-4,5-dihydronicotinonitriles (1) were readily prepared by the ternary condensation of malononitrile, salicylaldehyde (or 3-methoxysalicylaldehyde), and aliphatic ketones in the presence of ammonium acetate. The resulting 1 was transformed into the corresponding 3-carbamoyl derivatives (3) via their 2-acetamino derivatives (2). In addition, the reaction of 3 with acetic anhydride led to [2,3-d]pyridopyrimidine derivatives (4).
Stereospecific Syntheses and Acid Dissociations of 2,3-Diaminotetralins and 2,3-Diamino-trans-decalins
Authors: Yano Tairoku , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

cis- and trans-2,3-Diaminotetralins and 2(e), 3(e)-, 2(e), 3(a)-, and 2(a), 3(a)-diamino-trans-decalins were stereospecifically synthesized from 1,4-dihydronaphthalene and trans-Δ2-octalin, respectively. The stepwise acid dissociation constants of the decalin derivatives were determined by potentiometric method and discussed in relation to their configurations.
The Peroxide-induced Addition of Acetic Acid to Olefins
Authors: Suhara Yasuo
Published: July 2006

The peroxide-induced addition of acetic acid to ethylene gave straight-chain fatty acids, such as butyric, hexanoic, octanoic, decanoic, lauric, myristic, and palmitic acids. Some α-branched-chain fatty acids were also formed. Di-t-butyl peroxide (DTBP) was an effective initiator in forming fatty acids. To obtain the 1 : 1-telomer acids, it was preferable that a 20–10 : 1 : 0.25 (mol) mixture of acetic acid, ethylene, and DTBP be heated at 150°C for 6 hr. Straight-chain fatty acids were also obtained by the reaction of acetic acid to 1-olefins under similar conditions.
Photoreaction of 2,2-Diphenylvinyl Ketones
Authors: Maeda Kazuyuki , Moritani Ichiro , Sonoda Akio
Published: July 2006

The photoreaction of 2,2-diphenylvinyl ketones leading to 1,1,4,4-tetraphenylbutadiene, which seems to formally involve α-cleavage of vinyl ketones.
Preparation and Properties of Dimeric Dialkoxo-bridged Chromium(III) Complexes with 3-Bromo-2,4-pentanedione
Authors: Kasuga Kuninobu , Itou Tsunao , Yamamoto Yasuo
Published: July 2006

μ,μ′-Dialkoxotetraquis(3-bromo-3,4-pentanedionato)dichromium(III), where alkoxo is methoxo, ethoxo, n-propoxo or n-butoxo, has been prepared. These complexes have been identified by means of the elementary analysis, determination of molecular weight and the spectrometry.
Charge-transfer Complex of Sydnones
Authors: Chinone Akiko , Ohta Masaki
Published: July 2006

The complex formation of 3-methylsydnone, 3-phenylsydnone, and 3,4-diphenylsydnone with TGNE was described. From the electronic absorption spectra of the complexes, ionization potentials of sydnones are estimated.
Iminodithiocarbonates. VI. Reaction of Sulfur-substituted Carbonium Ion with Sodium Azide
Authors: Ueno Yoshio , Okawara Makoto
Published: July 2006

The reaction of 2-methylthio-1,3-dithiolan-2-ylium iodide 1 with sodium azide gave 2-methylthioimino-1,3-dithiolane 4. Thiooxime 4 reacted with chloramine T and dimethyl sulfate to give sulfilimine 9 and sulfonium salt 10, respectively.
Synthesis of Alkoxycyclopropane Derivatives, Intermediates in the Synthesis of Hirsutic Acid
Authors: Sakan Fujio , Sugiura Emiko , Matsumoto Takeshi , Shirahama Haruhisa , Hashimoto Hisanobu
Published: July 2006

The addition of several alkoxycarbeneson cis-bicyclo[3,3,0]octane derivative (2) was tried. The bulkier reagent gave the better stereoselectivity and exo adducts were obtained more predominantly.
The Chemistry of Protactinium. X. A Study of the Effect of Chromium (II) on the Solvent Extraction of Protactinium (IV), Using N-Benzoyl-N-phenylhydroxylamine, Tri-n-octylamine and Thenoyltrifluoroacetone as the Extractants
Authors: Kawasuji Isamu , Suzuki Shin
Published: July 2006

Cr(II) has been used for reducing protactinium in microquantities to the tetravalent state and for protecting it from re-oxidation. However, the effect of Cr(II) on the extraction behavior of Pa(IV) has not been taken into account by all of the previous investigators. On the basis of the above facts, the influence of Cr(II) on the extraction of Pa(IV) was studied by using such extractants as BPHA, TTA, and TOA. In every case, the distribution ratio of Pa(IV) decreased with an increase in the concentration of Cr(II) in the aqueous phase. One of the most reliable explanations for the phenomena is the possibility that a multi-nuclear complex between Pa(IV) and Cr(II) or Cr(III) is formed. However, the effect of Cr(II) on the absorption spectra of Pa(IV) could not be found, and many more experiments will be necessary to explain the effect of Cr(II) on the extraction behavior of Pa(IV).
Cycloaddition Reaction of Troponoids with Dimethyl Maleate
Authors: Takeshita Hitoshi , Shoji Yoshikazu , Itô Shô
Published: July 2006

Thermal cycloaddition reaction of methyl maleate with tropone, 2-chloro-, 2-methoxytropone and tropolone was investigated. Each reaction yielded [4+2] type adducts with high peri- and stereospecificities but with less regioselectivity.
Isotopic Study of Water Gas Reaction Catalyzed by Platinum
Authors: Masuda Makihiko , Miyahara Koshiro
Published: July 2006

By the use of 13C- and 18O-labelled carbon dioxide and D2 gas, water gas reaction over an evaporated Pt film was studied at temperatures 380–450 °C under constant elimination of water vapor with cold traps. The reaction of CO2 and H2 was as rapid as that of CO2 and D2, the mixture of H2 and D2 changing rapidly into an equilibrium mixture of H2, HD, and D2 in the course of the reaction with CO2. The mixture of C18O2 and CO2 was also rapidly equilibrated by the reaction with H2. The exchange reactions of 18O and 13C between CO2and CO in the course of the water gas reaction were similarly observed. The theory of the stoichiometric number on the rate-determining step was applied to the results. From the results and the observed rate equation of the water gas reaction, V=k[CO2]0.6[H2]−0.5, the reaction was supposed to be caused by the sequence of steps, CO2\ightleftharpoonsCO2(a), H2\ightleftharpoons2H(a), CO2(a)+H(a)\ightleftharpoonsX(a), X(a)\ightleftharpoonsCO(a)+OH(a), CO(a)\ightleftharpoonsCO, and OH(a)+H(a)\ightleftharpoonsH2O, and to be rate-controlled by the third and fourth steps, where (a) denotes the adsorbed state and X(a) is an intermediate to rule out the direct conversion of CO2(a)+H(a) into CO(a)+OH(a).
The Crystal Structure of the 1:1 Complex of Pyromellitic Dianhydride with trans-Stilbene
Authors: Kodama Toshiko , Kumakura Shigekazu
Published: July 2006

The 1: 1 complex of pyromellitic dianhydride with trans-stilbene crystallizes in the space group P21/c with two pairs of the component molecules in a unit cell with dimensions of a=12.48, b=6.33, c=13.17 Å, and β=111.6°. The structure was solved from a three-dimensional |E|2 Patterson synthesis and refined by a block-diagonal least-squares method to a final R value of 0.12 for 1635 reflections. In the trans-stilbene molecule, the plane containing the central ethylene group makes an angle of 11.5° with the phenyl plane. The non-planarity of the trans-stilbene molecule seems to be largely due to a steric repulsion between the hydrogen atom attached to the ethylene moiety and that at the 6 and 6′ position in the phenyl group. The pyromellitic dianhydride molecule is approximately planar. The component molecules are stacked alternately in infinite columns along the a axis. The average spacing between the phenyl plane of trans-stilbene and the molecular plane of pyromellitic dianhydride is 3.59 Å, and these palnes make an angle of 4.8° with each other. The relative arrangement of the component molecules in the crystal differs from that observed in the crystal of the anthracene, pyrene, or perylene complex with pyromellitic dianhydride. The van der Waals forces are considered to be more important than the charge transfer force in determining the relative arrangement of the component molecules in this crystal.
The Preparation and Characterization of Bis[2-(2-pyridyl)imidazole]iron(II) Complexes
Authors: Sasaki Yoshihiro , Shigematsu Tsunenobu
Published: July 2006

Bis[2-(2-pyridyl)imidazole]iron(II) complexes, Fe(PI)2X2 (X=C1−, Br−, NCS−, N3−, and CN−), were prepared and characterized on the basis of their infrared and Mössbauer spectra and their magnetic data. In Fe(PI)2(NCS)2 the NCS− groups are N-bonded and are in a cis position. Fe(PI)2(CN)2H2O also has a cis configuration about the CN− ligands. Except for Fe(PI)2(CN)2H2O, the magnetic moments of the complexes lie in the 4.94–5.27 B.M. range. Fe(PI)2(CN)2H2O is a diamagnetic compound.
Polarographic Studies of Dispersed Dyes Solubilized in Surfactant Solutions. I. Kinetics of Orange OT Solubilized in Surfactant Solutions
Authors: Suzuki Hajime , Shinozuka Noriko , Hayano Shigeo
Published: July 2006

Orange OT (l-o-tolyl-azo-2-naphthol) dissolved in an aqueous ethanol solution and solubilized in various surfactant solutions, containing a citric acid-disodium hydrogen phosphate buffer, showed well-defined irreversible polarographic waves. The anionic, cationic, and nonionic surfactants used were sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS), dodecyltrimethylammonium chloride (DTMAC), and polyoxyethylene nonylphenyl ether (NP-\bar10) respectively. The values multiplying the transfer coefficient by the number of electrons involved in the activation step, (αna), were calculated from the semilogarithmic plot of the wave. The plots of αna against the half-wave potential of Orange OT for each solution showed that a marked surfactant electric-charge dependence of αna was observed with a variety of surfactant solutions; i.e., the electric-charges of the surfactant molecules or micelles remarkably affected the electrode kinetics of the solubilized Orange OT. No matter what Orange OT is an uncharged species, Orange OT solubilized in the anionic surfactant solutions seemed to behave in the electrode process as if it were an anionic species, and when solubilized in the cationic and nonionic surfactant solutions it seemed to behave as a cationic species.
The Extraction of Tris(1,10-phenanthroline)ruthenium(II). I. Distribution Studies
Authors: Takamatsu Takejiro
Published: July 2006

Tris(1,10-phenanthroline)Ru(II) was extracted into various organic solvents with several anions, such as the perchlorate ion, the iodide ion, or the thiocyanate ion. The association constants of ion-pairs were successfully determined by analysis of the extraction curves in the solvents with low polarities. It was found that the ion-pairs were extracted mainly as the associated form and that only the first-step dissociation could slightly occur (<10−7) in such solvents; furthermore, the degree of association was considerable even in water. Therefore, the distribution ratio of the complex cation must be governed by both the hydration energy of the counter anion and the solubility parameter of the extraction solvent rather than its dielectric property. An abnormal decrease in the distribution ratio was observed when the tetraphenylborate ion was used as the counter anion. This phenomenon can be explained clearly in terms of the hydrotropism which was often encountered in the solution of an electrolyte with a large ion.
Study in Some Heterochelates. III. Cu(II), Ni(II), Zn(II) or Cd(II)+Histidine or Ethylenediaminetetraacetic Acid+Polyphenols Systems
Authors: Mavani I P , Jejurkar C R , Bhattacharya P K
Published: July 2006

An extension of Irving-Rossotti technique has been applied to study the formation constant of mixed ligand complexes as follows:

[MA]+[L]\ightleftarrows[MAL]

where M=Cu(II), Ni(II), Zn(II), and Cd(II), A=histidine or ethylenediaminetetraacetic acid and LH2= catechol, pyrogallol or 2,3-dihydroxynaphthalene. The values obtained for the mixed ligand formation constants KMAL are found to be less than the first formation constant KML, in the binary systems.
ESR Spectra of Quadridentate Salicylaldehyde Schiff Base Complexes of Cobalt(II) and Copper(II) in Chloroform and in Dichloromethane
Authors: Chikira Makoto , Kawakita Toshio , Isobe Taro
Published: July 2006

ESR parameters for the titled complexes have been obtained from the spectra of “powders of frozen solutions.” The spectra of “not crushed frozen solutions” indicated that the axes of g3 (3.23—3.68) of the cobalt complexes are in the molecular planes.
Solubility Studies of Ion-pairs in Organic Solvents
Authors: Takamatsu Takejiro
Published: July 2006

The solubilities of several types of ionpairs were measured in many organic solvents at 25 °C. A good correlation holds between the logarithmic solubilities and the solubility parameters of solvents over the whole range of polarity.
The Application of the Regular Solution Theory to the Ion-pair Systems
Authors: Takamatsu Takejiro
Published: July 2006

The solubilities of these ion-pairs, KCl, KBr, and KI, were measured in alcohols. The logarithmic solubilities could be well correlated with the solubility parameters of the solvents.
Synthetic Studies of Amino Acids by the Use of Copper(II) Complexes. V. The Preparation of Hydroxy Amino Acids by a Set of Improved Procedures
Authors: Ohdan Shohji , Ighikawa Tetsuya , Araki Younosuke , Ishido Yoshiharu
Published: July 2006

A variety of hydroxy amino acids were prepared by a brief treatment of a resulting mixture, which was obtained by a base-catalyzed condensation reaction of N-pyruvylideneglycinatoaquocopper(II) with aldehydes, on a column of Amberlite IR-120B (H form) resin.
Reaction of N-Nitroso-1,2,3,4-tetrahydroisoquinolines with Base. A New Method for the Conversion of 1,2,3,4-Tetrahydroisoquinolines into 3,4-Dihydroisoquinolines
Authors: Sakane Kazuo , Terayama Ken-ichi , Haruki Eiichi , Otsuji Yoshio , Imoto Eiji
Published: July 2006

Treatment of N-nitroso-1,2,3,4-tetrahydroisoquinoline (2a) and its 1-methyl derivative (2b) with base gave the corresponding 3,4-dihydroisoquinolines (3a and 3b). However, similar treatment of N-nitroso-1,2,3,4-tetrahydroisoquinoline-1-acetic acid (2c) gave a mixture of 3b and 1,2,3,4-tetrahydroisoquinoline-1-(α-hydroxyimino)acetic acid (4).
Synthesis of (4-Pyridyl)-1,2-ethanediol
Authors: Aaron Herbert S , Miller Jacob I
Published: July 2006

A conflict in the literature regarding the physical properties of 4-(pyridyl)-1,2-ethanediol has been resolved. The melting point and solubility data of this compound are correct as reported in J. Org. Chem., 30, 1331 (1965).
A Study of Catalysis by Metal Phosphates. II. A Kinetic Study of the Dehydrogenation of 2-Propanol over the Cadmium Phosphate Catalyst and an Investigation of the Acid-base Character of the Catalyst
Authors: Nozaki Fumio , Ohta Haruo
Published: July 2006

The dehydrogenation of 2-propanol over the ortho cadmium phosphate catalyst has been investigated by means of a conventional tubular-flow reactor operating at atmospheric pressure. The adequate temperature for the calcination of catalyst was about 400 °C. The reaction-rate data were approximately arranged by Eq. (3), using the Langmuir-type expression described in the text. The catalytic activity for dehydrogenation to acetone was completely poisoned by the addition of a small amount of CCl3COOH during the course of the reaction, whereas the activity for dehydration to propylene was greatly enhanced. The behavior of CH2ClCOOH and C6H5COOH as poisons was also investigated. C5H5N had no effect on the catalytic reaction. It has been concluded that the cadmium phosphate is to be characterized as a basic catalyst.
Optical Resolution and Racemization of Tris(acetylacetonato)germanium(IV) in Organic Solvents
Authors: Nagasawa Akira , Saito Kazuo
Published: July 2006

The tris(acetylacetonato)germanium(IV) has been resolved by the crystallization of its hydrogen-R,R-di-benzoyltartrate in a mixture of acetonitrile, ethanol, and water. The racemization kinetics of perchlorate of the Δ-enantiomer has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane, acetonitrile (AN), and N,N-dimethylformamide, the activation enthalpies (ΔH\eweq/kacl· mol−1) and the activation entropies (ΔS\eweq/cal· K −1 mol−1) being 27.9, 26.6, 24.3, and 23.3, and +3.7, −1.1, −4.4, and −5.0, respectively. The ligand isotopic exchange is much slower than the racemization under similar conditions. Consideration of acid (in TCE) and base (in AN) catalysis, influence of ionic strength and solvent effect suggests an intra-molecular mechanism via an intermediate in which one of the ligands is in unidentate state.
A Photo-selection Study of the Charge-transfer Phosphorescence
Authors: Amano Takako , Kanda Yoshiya
Published: July 2006

The polarization of the charge-transfer phosphorescence has been studied by the method of photo-selection. It has been measured relative to the electric vector of the excitation light corresponding to the charge-transfer band in wavelength for the complexes of tetracyanobenzene, o-, m-, and p-dicyanobenzenes, tetrachlorophthalic anhydride, and phthalic anhydride as electron acceptors, and methyl-substituted benzenes as electron donors, in organic glass at 77 K. It has been shown that the degree of polarization through excitation into the charge-transfer band is almost constant in the phosphorescence region, while it gradually decreases as the ionization potential of the donor increases for any of the acceptors. These observations can reasonably be interpreted in terms of a model in which the charge-transfer phosphorescence is polarized normal to the molecular plane, irrespective of the complex, and in which the change in the polarization degree of the charge-transfer phosphorescence is responsible for the change in the direction of the transition moment of the charge-transfer absorption band.
Medium Effects for Single Ions in Dimethyl Sulfoxide, N,N′-Dimethylformamide, and Propylene Carbonate
Authors: Matsuura Niro , Umemoto Kisaburo
Published: July 2006

The solubility products of thallium halides were measured in dimethyl sulfoxide, N,N′-Dimethylformamide, and propylene carbonate for the purpose of obtaining the values of the medium effect for these electrolytes on transfer from water to these solvents. The medium effects for cations were estimated from the standard potentials of metal/ion couples obtained by the method of the corrected rubidium scale. The medium effects for halide ions were calculated from the medium effects for thallium halides and the thallium ion. A comparison of extrathermodynamic assumptions was made for the values of the medium effect for the silver ion as estimated by various methods ; the method of the corrected rubidium scale was found to give a reasonable result.
Anomalous Light Scattering by Poly(2-vinylpyridine) in Methanol
Authors: Sakamoto Noriyuki , Yoshida Masafumi , Arichi Shizuo
Published: July 2006

The light scattering of a poly(2-vinylpyridine) solution was measured under various conditions. In solvents such as methanol, ethanol, 2-propanol, 2-butanone, and pyridine, anomalous Zimm plots with an upward inflection at lower angles were observed. This anomaly was especially striking in methanol, in which the dissymmetry coefficient was frequently less than unity. Systematic investigations carried out with methanol as a solvent revealed that; (1) the anomaly does not depend appreciably on the concentration or tacticity of the polymer, the temperature, or the wavelength of the incident light; (2) the anomaly diminishes with an increase in the molecular weight of the polymer; (3) the anomaly disappears upon the addition of dry ammonia of 10−2 mol/1 or more in methanol, and (4) similar perturbed Zimm plots are realized by the addition of a trace amount of hydrochloric acid or sulfuric acid in a methanol solution of a higher-molecular-weight fraction which showed a normal Zimm plot in pure methanol. The anomaly can not be explained in terms of the effects of the optical anisotropy of the polymer segment, but the external interference arising from the non-random arrangement of the polymer in solution may contribute to it.
The Crystal Structure of dl-1,2,3,4,5,6-Hexahydro-6,11,12,12-tetramethyl-2,6-methano-3,11-propano-3-benzazocine Hydrochloride Monohydrate
Authors: Kimura Michio , Nakajima Takesi , Inaba Shigeho , Yamamoto Hisao
Published: July 2006

The structure of the title crystal (C19H27N·HCl·H2O) has been determined by X-ray diffraction method. The racemate crystallizes in monoclinic, space group P21/c with a=14.30, b=15.74, c=7.79Å, β=98°58′ and Z=4. The reflection intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKx radiation. The structure was solved by the direct method of phase determination. The final R factor was 0.113. The molecules are linked in endless chains along c-axis by N+···Cl− and Cl−···H2O···Cl− hydrogen bonds. Two piperidine rings in the molecule have the chair conformation. This product which shows analgesic activity has a new molecular structure having a four-ring system, part of which is a benzomorphan nucleus.
Studies of Ruthenium Complexes. VII. Photochemical Reactions of cis-Dihalogenotetraammineruthenium(III) Complexes in Aqueous Solutions
Authors: Ohyoshi Akira , Takebayashi Noriyuki , Hiroshima Yutaka , Yoshikuni Kenichiro , Tsuji Kazuhiko
Published: July 2006

Studies have been made of the photochemistry of cis-dihalogenotetraammineruthenium(III) in aqueous solutions. For the cis-dichlorocomplex, no photochemical reaction has been observed by the irradiation of the visible light region. For cis-dibromo- and cis-diiodo-complexes, a simple aquation of halide ligand seems to occur in a solution with a pH lower than 2.5. The typical values of the quantum yields for the cis-[RuX2(NH3)4] ++H2O\xrightarrowhν cis-[RuX(OH2)(NH3)4]2+X− reaction were 0.27×10−2 (382 nm light) and 0.82×10−2(408 nm light) for dibromo- and dichloro-complexes respectively. The quantum yield was dependent on the wavelength of light, but was independent of the concentrations of halide and hydrogen ions. The quantum yield seems to depend on the oxidizability of the ligand or on probability of the deactivation process in the primary excited state. In accounting for the low quantum yield, it seems most probable that the photoexcited complex species is converted to the ground state by non-radiative transitions.
Electron Transfer Reaction between Thallium(I) and Thallium(III) in the Presence of Cerium(IV) in Aqueous Solution
Authors: Wada Goro , Tamaki Kyoko
Published: July 2006

The kinetics of the electron transfer reaction between Tl(I) and Tl(III) was investigated in the presence of Ce(IV) by use of a radioactive tracer 204Tl. The apparent rate constant of the reaction, kapp, was dependent upon [H+] and [Co(IV)] (<0.6×103 M) and can be expressed by

k_app=k_A+\frack_B[H^+]+\left(k_C+\frack_D[H^+]\ight)[Ce(IV)].

k app is gradually saturated to a limiting value according to [H+] at higher [Ce(IV)]. The observed values are kA=4.70 M−1 h−1, kB=2.13 h−1, kC=1.30×103 M−2 h−1 and kD=2.61×103 M−1 h−1 at 50 °C. Since Ce(IV) is a one-electron-oxidant, Tl(I) is oxidized by one-electron transfer to produce Tl(II) as an intermediate. However, in the absence of one-electron-oxidant or -reductant, two electrons are transferred from Tl(I) to Tl(III) not through double steps of one-electron transfer but predominantly through a single step of two-electron transfer.
Kinetics of Multidentate Ligand Substitution Reactions. XVI. Substitution Reactions of l,2-Cyclohexanediamine-N,N,N′,N′-tetraacetic Acid (CyDTA) with the Zinc(II)–Ethylenediaminemonoacetate (EDMA) and -Ethylenediamine-N,N′-diacetate (EDDA) Complexes and That of Ethylenediamine-N,N,N′,N′-tetraacetic Acid (EDTA) with the Nickel(II)–EDDA Complex
Authors: Kodama Mutsuo
Published: July 2006

The kinetics of the substitution reactions of CyDTA with zinc(II)–EDMA and –EDDA complexes and that of EDTA with the nickel(II)-EDDA complex were studied systematically by using the polarographic technique. All the substitution reactions were found to be first-order with respect to the CyDTA or EDTA anion and also first-order with respect to the 1 : 1-ratio EDMA or EDDA complex. From a comparison of the observed rate constants with those estimated on the basis of the proposed reaction intermediates, the detailed reaction mechanisms were discussed. The rates of the reactions of zinc(II)–EDMA complex and nickel(II)–EDDA complex could be understood in terms of the ethylenediamine reaction mechanism, but that of the reaction of the zinc(II)–EDDA complex with the CyDTA anion could not. This discrepancy may be ascribed by the steric hindrance of the CyDTA anion to the formation of an ethylenediamine reaction intermediate in the reaction of the zinc(II)–EDDA complex.
Cobalt-59 Nuclear Magnetic Resonance Study of Cobalt(III) Complexes. Empirical Rules for the Cobalt-59 Chemical Shifts and Line Widths of [CoIII(en)x(NH3)6−2x−yLy]-type Complexes
Authors: Yajima Fumikazu , Koike Yasuo , Yamasaki Akira , Fujiwara Shizuo
Published: July 2006

The cobalt-59 chemical shifts and line widths for about seventy cobalt(III) complexes of the [CoIII(en)x(NH3)6−2x−yLy] (L= Cl, Br, NO2, N3, OH, H2O, CO3, and C2O4) type have been measured. The cobalt-59 chemical shifts of this type of complex are approximately represented by a simple relation:

δ(ppm)=360x+\oversety\underseti=1∑δ_i(L) (x=0, 1, and 2),

where δi(L) is the i-th ligand shift parameter which represents the contribution of the i-th ligand, l, to the total chemical shift. Three empirical rules can be derived from experimental observations: I. The chemical shift of a trans-isomer is higher than that of the corresponding cis-isomer. II. The line width of the trans-CoA4B2 isomer is larger than that of the cis-CoA4B2 isomer. III. The line width of a meridional isomer is larger than that of the corresponding facial isomer. Illustrative examples are presented where cobalt-59 NMR is used to identify cobalt (III) complexes and to study the kinetics and equilibrium in solution.