Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 6
Showing 1-50 articles out of 78 articles from the selected issue
  • Shigeo Hayano, Noriko Shinozuka
    1969 Volume 42 Issue 6 Pages 1469-1472
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The apparent mean particle size of the solubilized dye in nonionic surfactant solutions is determined from the polarographic diffusion coefficient. The diffusion coefficient and the particle size obtained are in good agreement with those of the nonionic surfactant micelle reported in the literature. For the system of polyoxyethylene nonylphenyl ether (NP-\bar19) and 1,4-diaminoanthraquinone, the particle size increases with the dye concentration; however, the particle size is almost constant for the system of NP-\bar19 and 1,4,5,8-tetraaminoanthraquinone (TAA). When a certain quantity of TAA is solubilized into the 10−3–10−2M NP-\bar19 solution, the particle size is also constant. In the case of the polyoxyethylene lauryl ether (LA-\bar14) and TAA system, the particle size markedly decreases with the increase in the dye concentration. This tendency suggests that the numbers of micelles increase with the concentration of the solubilizate. The fact that the half-wave potential of the dye reduction is independent of the concentration of the surfactants is explained in terms of the similarity between the electrode process of the solubilized dye and that of the dissolved dye.
  • Osamu Kikuchi
    1969 Volume 42 Issue 6 Pages 1472-1475
    Published: 1969
    Released: March 27, 2006
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    The spin distributions and g factors have been calculated for seveial aromatic nitric oxide radicals. The spin distributions calculated by the open-shell SGF method with configuration interaction, and by the unrestricted SCF method with the annihilation of the quartet component from the single determination wave function, agreed with the experimental values estimated from the ESR spectra. The contributions of the lone-pair orbital of the oxygen and of the N–O σ-bonding orbital to the g factor were calculated, the calculated g factors in solution being in the range of 2.005–2.006; these values were then discussed on the basis of the electronic structures of nitric oxide radicals.
  • Masaji Miura, Yukio Kubota, Toru Iwaki, Kazuto Takimoto, Yoshinori Mur ...
    1969 Volume 42 Issue 6 Pages 1476-1480
    Published: 1969
    Released: March 27, 2006
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    The acidity and the acid strength of the sites of such solid catalysts as silica gel, alumina, and silica-alumina were determined by the n-butylamine titration method using the Hammett indicators. The distribution of the acid sites on the surfaces of these catalysts was found to vary with the outgassing temperature, and also with the alumina content in the case of silica-alumina. The heats of immersion of these catalysts in water and in an aqueous solution of n-butylamine were measured. The heat value corresponding to the difference between these two cases, as well as the number of acid sites, showed a maximum at contents of 10–20%. These phenomena are discussed with reference to the results of the diffuse reflection measurements.
  • Tomohiko Hirooka, Masakatsu Kochi, Jun-ichi Aihara, Hiroo Inokuchi, Yo ...
    1969 Volume 42 Issue 6 Pages 1481-1486
    Published: 1969
    Released: March 27, 2006
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    The photoemission from various types of charge-transfer complexes, quinolinium-tetra-cyanoquinodimethane Q(TCNQ2 (I), dibenzophenothiazine (DBP)-dicyanodichloro-p-benzoquinone (DDQ)[(DBP)(DDQ)(II) and (DBP)2(DDQ)(III)], trinitrobenzene (TNB)-coronene (IV), and TNB-perylene (V),and also large polycyclic aromatic hydrocarbons, violanthrene A (VI), violanthrene B (VII), coronene (VIII), pyranthrene (IX), and pyranthrone (X), was observed in the vacuum ultraviolet region. The experimental equation Y ∝(EE*)3, where Y is the quantum yield of photoemission; E, the incident photon energy, and E*, the threshold energy, was used to determine the ionization potential. The E*-values, as estimated from the experimental equation, were I=4.85 eV, II 4.99, III 4.75, IV 5.62, V 5.52, VI 5.06, VII 5.13, VIII 5.58, IX 5.04, and X=5.71 eV. A band structure scheme for these organic semiconductors was introduced to analyse the emission mechanism.
  • Sumio Ichiba, Mitsuo Mishima, Hisao Negita
    1969 Volume 42 Issue 6 Pages 1486-1489
    Published: 1969
    Released: March 27, 2006
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    The Mössbauer spectra of molecular complexes of tin(IV) chloride with some oxygen-containing aromatic compounds, such as hydroxybenzaldehydes and cinnamic acid, were investigated. Most of these complexes show the quadrupole splitting resulting from the addition of aromatic molecules to tin(IV) chloride, although in some cases broad absorption curves are observed. The isomer shifts of these complexes are 0.25—0.45 mm/sec, much smaller than that of tin(IV) chloride itself. These values are almost the same as those of the complexes of tin(IV) chloride with aliphatic compounds. From these results, the bond nature and structures of these complexes, which had not previously been studied, were discussed in some detail.
  • Tetsuo Morimoto, Noriko Katayama, Hiromitu Naono, Mahiko Nagao
    1969 Volume 42 Issue 6 Pages 1490-1493
    Published: 1969
    Released: March 27, 2006
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    Four kinds of ferric oxide (α-Fe2O3) which differ in origin and history have been used for measurements of the surface area, the water content, and the heat of immersion in water. Two cases have been discovered; in one there appears a maximum in the plot of the heat of immersion against the pretreatment temperature according to the origin of the sample, but in the other a maximum does not appear. The heavy hydration treatment carried out prior to the immersion measurements raises the value of the heat of immersion in water, but it has no serious effect on the heat of surface hydration calculated therefrom, as in the case of TiO2. The average value of the latter was 11.3 kcal/mol H2O.
  • Kenji Ishida
    1969 Volume 42 Issue 6 Pages 1493-1497
    Published: 1969
    Released: March 27, 2006
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    It has been shown that the relaxation process in a system of noninteracting particles in contact with a heat bath, on the assumption that the system is in local equilibrium, can be described by the Markov process homogeneous in time, and that the solution of the Markov process is a multinomial distribution. The nonequilibrium thermodynamics for such a relaxing system was formulated by means of the stochastic entropy production which can be derived by the probabilistic version of classical entropy production. As a special case, the stochastic nonequilibrium thermodynamics for the relaxing system of identical harmonic oscillators was discussed.
  • Tadayoshi Sakata, Saburo Nagakura
    1969 Volume 42 Issue 6 Pages 1497-1503
    Published: 1969
    Released: March 27, 2006
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    The electronic absorption spectra of Würster’s Blue perchlorate and N-ethylphenazyl in solid were measured at various temperatures ranging from 48°K to 300°K. In both cases, strong bands due to the charge-transfer between the half occupied orbitals of respective component radicals were observed in near infrared region. This assignment of these bands was supported by the polarized absorption measurement carried out with the Würster’s blue perchlorate single crystal. The charge-transfer band of solid Würster’s blue perchlorate was found to increase its intensity with decreasing temperatures; in particular, the increasing tendency became predominant below the phase transition point (186°K). The similar tendency was also observed for solid N-ethylphenazyl. The temperature dependence of the band was found to be closely related with the population of triplet excitons determined from the measurement of magnetic susceptibility or paramagnetic resonance. The separation J between the ground singlet state and the thermally accessible triplet state was determined from the analysis of the temperature dependence of the charge-transfer band to be 235 cm−1 and 320 cm−1 for Würster’s blue perchlorate and N-ethylphenazyl, respectively.
  • Jiro Okamoto, Enzo Tachikawa
    1969 Volume 42 Issue 6 Pages 1504-1509
    Published: 1969
    Released: March 27, 2006
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    82Br obtained via the (I. T.) process has been reacted with methyl bromide. In the gaseous phase, only CH382Br and CH282BrBr are observed as major products, whereas in the solid phase other products, such as CH82BrBr2 and C2H582Br, have also been observed. Moderator experiments using He or Xe indicate that the formations of both CH382Br and CH282BrBr involve the reactions of the energetic 82Br atom. This is in great contrast to the early observations of the Br2-CH4 system, where the ionic as well as the energetic reactions of 82Br play a role in the formation of the C-82Br bond. Comparisons of these results with those found in the reactions of the 80Br obtained via the (n, γ) process suggest that the Br atom obtained via the (n, γ) process is more electronically excited than that from the (I. T.) process. The kinetic analysis of the present results gives the following relative α-values: αHe, 1.0; αXe, 8.8; αCH3Br, 10.3. It is suggested that, during the cooling-down process of 82Br, a high inelasticity is involved in the collision of 82Br, even with monatomic molecules.
  • Kinya Iijima, Isao Oonishi, Fumio Muto, Akitsugu Nakahara, Yoshimichi ...
    1969 Volume 42 Issue 6 Pages 1509-1514
    Published: 1969
    Released: March 27, 2006
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    A new copper(II) chelate of the Schiff base derived from pyruvic acid and ethanolamine has been prepared. The crystal structure of this complex, [Cu(pyv=etham)2]·4H2O, has been determined from three dimensional X-ray diffraction data. The dimensions of monoclinic cell are a=6.50Å, b=19.75Å, c=7.26Å, β=113.0° and Z=2. The space group is P21n. The structure has been refined by three dimensional difference syntheses to R=0.126. It has been disclosed that copper (II) links to the 2-hydroxyethyliminopyruvate anion through the terminal carboxylate group, and the nitrogen of the Schiff base linkage. Having a center of symmetry, the complex molecule is in the trans-configuration and has normal bond distances and angles. The coordination around copper(II) is square planar; the Cu–O and Cu–N distances are 1.92 and 2.00Å, respectively. Two additional oxygen atoms of the water molecules at 2.57Å complete a distorted octahedron around copper(II). The complex molecules are held together in the crystal by the O–H···O hydrogen bonds, forming a three dimensional network.
  • Satoru Tsuda, Akira Yokohata, Michihiro Kawai
    1969 Volume 42 Issue 6 Pages 1515-1518
    Published: 1969
    Released: March 27, 2006
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    The studies of this series were extended to the negative ions of me 26 and 42 obtained from nitroalkanes; nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. For me 26 (probably, CN) ions, the contribution of three or two processes in the range from zero to ∼20 eV of electron energy was observed for nitromethane or other samples. On the basis of ΔHf values of the reactants and products, and of the value of EA(CN), the plausible reactions to be assigned to each process were presented. For the first process, CH3NO2+e→CN+H2O+OH, RNO2+e→CN+R1OH+OH. For the second process, CH3NO2+e→CN+H2O+O+H, CH3NO2+e→CN+H2+O2+H, RNO2+e→CN+R1+HO2+H, and C3H7NO2+e→CN+C2H4+H2+O+OH irrespective of kind of nitropropane. For the third process, CH3NO2+e→CN+3H+O2. For me 42 (probably, CNO) ions, the contribution of two processes was observed. By taking ΔHf (CNO)=x (eV), EA(CNO)=y (eV), and also combining the observed onset values with the calculated values of appearance potential of reactions to be assigned for each process — for the first process, CH3NO2+e→CNO+H2+OH, RNO2+e→CNO+R1OH+H; for the second process, CH3NO2+e→CNO+HO+2H, CH3NO2+e→CNO+H2+O+H, RNO2+e→CNO+R1O+2H– a relation of xy\simeq2(eV) was derived.
  • Koji Nobutoki, Hiroshi Sumitomo
    1969 Volume 42 Issue 6 Pages 1519-1524
    Published: 1969
    Released: March 27, 2006
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    Polystyrene ketone possessing a benzophenone structural unit in the middle part of the chain was synthesized by the coupling reaction of one-ended living polystyrene with 2,4′-dichlorobenzophenone. Polystyrene ketone potassium ketyl was prepared by the reaction of polystyrene ketone with an equivalent amount of potassium naphthalene complex in tetrahydrofuran. Polystyrene ketone potassium dianion was also formed with excess potassium in the solvent. These polystyrene ketone potassium adducts induced a quantitative polymerization of metyl methacrylate. Gross polymer from each of the reaction systems was elution-fractionated into four fractions in which a new class of star-type graft copolymer was included together with polystyrene and polymethyl methacrylate. Each fraction was characterized by means of the measurements of the yield, molecular weight and styrene content. Consideration was also made on a possible mechanism of the polymerization.
  • Akio Kosaki, Hiroshi Suga, Syûzô Seki, Kazuo Mukai, Yasuo ...
    1969 Volume 42 Issue 6 Pages 1525-1530
    Published: 1969
    Released: March 27, 2006
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    Measurements of heat capacity of Galvinoxyl radical and its phenol derivative were carried out in the temperature region from 12 to 300°K. Galvinoxyl radical exhibits a phase transition of first-order nature at 81.5°K which corresponds to the susceptibility anomaly already measured. The enthalpy and entropy of transition amount to 1504.6 J/mol and 18.67 J/(°K·mol), respectively. The entropy change, which corresponds formally to R In 9.45, cannot be explained by taking only the magnetic contribution. On the other hand, its phenol derivative, the corresponding diamagnetic substance, has not thermal anomaly in the above temperature region. X-Ray diffraction patterns at room temperature for both substances agree well with each other in their diffraction angles. From these experimental findings, it seems to be plausible that a kind of transformation of the crystal structure of Galvinoxyl radical takes place at the transition point which may be induced by a pairing of magnetic spins between neighboring molecules.
  • Shigeru Tsunashima, Shin Satoh, Shin Sato
    1969 Volume 42 Issue 6 Pages 1531-1533
    Published: 1969
    Released: March 27, 2006
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    Using the cadmium-photosensitized cis-trans isomerization of cis-2-butene, the lifetime of triplet benzene has been estimated to be of the order of 10−5 sec for both benzene-d0 and -d6. This technique provides a new method for measuring the lifetime of the triplet state of some molecules.
  • Yoshio Nakamura, Fumio Oki, Hiroshi Nozaki
    1969 Volume 42 Issue 6 Pages 1534-1538
    Published: 1969
    Released: March 27, 2006
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    The mechanism of deposition was investigated using maleic-linseed oil as a sample. The deposition was made by a constant voltage or by continuous pulses with high voltages, and the initial current-time relations were observed by means of a synchroscope. When we applied pulses with α⁄β values which were smaller than a value, the current decreased gradually after some time and a deposited film was found on the anode, but the decreases in the current was not found for a long time when the value of β was much larger than the value of α. The induction time was found from the current-time curve observed during a constant voltage deposition. These results were discussed from the standpoint that the deposited film is formed by coagulation resulted from ionic combination with hydrogen ions.
  • Toyozo Uno, Katsunosuke Machida, Yutaka Saito
    1969 Volume 42 Issue 6 Pages 1539-1545
    Published: 1969
    Released: March 27, 2006
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    The infrared spectra between 4000 and 33 cm−1 of biuret-hydrate and between 4000 and 250 cm−1 of its deuterated compound have been recorded. The vibrational assignments have been made by referring to the infrared spectra of the related compounds and the isotopic frequency shift. Normal coordinate analysis of the in-plane vibrations of biuret and biuret-d5 as twelve-body problem has been carried out by using the molecular model of the planar trans-cis conformation. A simple Urey-Bradley force field has been employed and the force constants have been refined by the least squares method. The calculation of potential energy distributions has shown that the NH in-plane deformation and the CN stretching vibrations couple appreciably with each other and give the imide II and III bands at 1515 and 1365 cm−1, respectively, just as in the case of diacetamide.
  • Nobuo Tanaka, Tamaichi Ashida, Yoshio Sasada, Masao Kakudo
    1969 Volume 42 Issue 6 Pages 1546-1554
    Published: 1969
    Released: March 27, 2006
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    The crystal structure of riboflavin hydrobromide monohydrate has been determined by a three-dimensional X-ray analysis. The space group is P 212121 with four formula units in the unit cell of dimensions a=18.28, b=6.99 and c=14.77 Å. The structural parameters were refined by means of a block-diagonal least-squares method, the final R factor being 0.07. The ribitol does not form a furanose ring but a chain. The protonation of the isoalloxazine ring occurs at the N(1) atom, and the C(4a)-N(10) bond is found to be a double bond. The bromide ion is situated midway between two isoalloxazine rings separated by a period along the b axis.
  • Takao Umegaki, Hiroshi Ito, Taijiro Okabe
    1969 Volume 42 Issue 6 Pages 1555-1558
    Published: 1969
    Released: March 27, 2006
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    The applicability of wet-process phosphoric acid containing such impurities as Al3+, Ca2+, Fe3+ and SO42− was examined. From the viewpoint of the corrosion resistivity of the phosphate coating, Al3+ ion was found to be the most undesirable contaminator. NaF was recognized as the most effective masking reagent for an elimination of Al3+ hindrance. SO42− also affected the phosphate coating formation, but the presence of less than 1% SO42− did not disturb the coating formation when an appropriate amount of accelerator was added to the phosphatizing solution.
  • Hajime Ishii, Hisahiko Einaga
    1969 Volume 42 Issue 6 Pages 1558-1561
    Published: 1969
    Released: March 27, 2006
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    A method was established for the spectrophotometric determination of microgram amounts of nickel after the extraction of nickel(II) as a salicylidene-o-aminophenol (SAP) complex from an alkaline aqueous solution into chloroform. Nickel(II) reacts with SAP to form a complex which can be extracted into organic solvents such as benzene, chloroform, methyl isobutyl ketone, etc., in the presence of ammonium ions. The extraction of nickel was almost quantitative, and a maximum and constant absorbance was obtained in the pH range from 8.5 to 9.8. The complex extracted was very stable and had an absorption maximum at 418 mμ. The composition of the complex was confirmed to be 1 to 1 (metal to ligand). A linear relationship was maintained between the concentration of nickel and the absorbance. The molar extinction coefficient and the sensitivity for log(I0I)=0.001 at 418 mμ were 17000 and 3.5×10−3 μg Ni/cm2, respectively. Several ions such as cobalt(II), copper(I and II), chromium(III), lead(II), manganese-(II) and citrate interfered with the determination.
  • Tsuneo Shimizu
    1969 Volume 42 Issue 6 Pages 1561-1569
    Published: 1969
    Released: March 27, 2006
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    Based on the analyses of 105 individual samples and 5 composites, totaling 158 rock samples, the following averages of scandium for various types of Japanese igneous rocks have been obtained (in ppm): granites 5.6, granodiorites 7.4, liparites 6.1, quartz diorites and diorites 11.4, dacites 14.1, andesites 21.8, gabbros 26.9, basalts 27.2 and ultramafic rocks 9.5. Scandium is determined by a combined ion-exchange-spectrophotometric method. Using Poldervaart’s suggested ratio of rock types, an abundance figure of 17 ppm Sc for the crust is suggested. The results on the abundance values for scandium in various types of igneous rocks confirm generally the figures given by Norman and Haskin in 1968. Analyses are also performed on Pacific oceanic sediments, giving as averages 18.7 ppm Sc for 4 red clays, 12.1 ppm Sc for 2 volcanic muds and 13.1 ppm Sc for 2 globigerina oozes. Brief discussion on the geochemistry of scandium is given.
  • Yuki Fujii, Eishin Kyuno, Ryokichi Tsuchiya
    1969 Volume 42 Issue 6 Pages 1569-1572
    Published: 1969
    Released: March 27, 2006
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    The following chromium(III) complexes containing N,N′-ethylenediaminediacetic acid (EDDA) were newly prepared: [Cr(Hedda)2]Cl·3H2O (red) (I), [Cr2(OH)2(edda)2]·6H2O (purple) (II), H[Cr(edda)(ox)]·2H2O (purple) (III), [Cr(edda)(dip)]I·5H2O (orange) (IV), K[Cr(NCS)2(edda)]·H2O (reddish purple) (V) and [Cr(Cl)(edda)(H2O)]·3H2O (bluish purple) (VI), where edda, ox and dip are the abbreviations of the N,N′-ethylenediaminediacetate and oxalate anions, and α,α′-dipyridyl respectively. On the basis of the experimental results, it was concluded that EDDA is coordinated as a terdentate ligand in complex I and as a quadridentate in the other complexes prepared in the present work. Furthermore, it was also suggested that complex II has a dimer structure and complex V has trans configuration (with respect to the coordinated carboxylate oxygen).
  • Hitoshi Ohtaki
    1969 Volume 42 Issue 6 Pages 1573-1578
    Published: 1969
    Released: March 27, 2006
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    Equilibrium of hydronium ions with alkoxonium ions in water-alcohol mixtures being taken into account, solvent effects on dissociation constants of acids were quantitatively interpreted by the following: free energy changes on transferring ions from an aqueous solution to a mixed solvent and difference in standard states in different solvent compositions. Choosing suitable values for effective ionic radii for ions involved, satisfactory agreements were found between experimental and calculated values of ΔpK, the difference of pK in water and in an aqueous mixture, for positively charged acids (e.g., ammonium, anilinium, etc.) as well as neutral acids yielding a negatively charged conjugate base (e. g., acetic acid, benzoic acid, p-nitrophenol, etc.).
  • Hiroshi Ogino, Toshiyuki Baba, Nobuyuki Tanaka
    1969 Volume 42 Issue 6 Pages 1578-1583
    Published: 1969
    Released: March 27, 2006
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    Kinetics of the substitution reactions of zinc(II) with meso-butylenediaminetetraacetatocobaltate(II) (cobalt(II)-meso-BDTA) and propylenediaminetetraacetatocobaltate(II) (cobalt(II)-PDTA) have been studied. The reaction of zinc(II) with cobalt(II)-meso-BDTA complex proceeds through two simultaneous reaction paths involving the acid dissociation reactions of the cobalt(II) complex. On the other hand, the reaction of zinc(II) with cobalt(II)-PDTA proceeds through four simultaneous reaction paths, of which two involve electrophilic substitution reactions and the others, the acid dissociation reactions of the cobalt(II) complex. This kinetic behavior is discussed on the basis of the natures of the ligands.
  • Norio Koine, Naokazu Sakota, Jinsai Hidaka, Yoichi Shimura
    1969 Volume 42 Issue 6 Pages 1583-1588
    Published: 1969
    Released: March 27, 2006
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    Eleven new complexes, trans(N)- or cis(N)-isomers of (ammoniatriacetato)(amino-acidato)cobalt(III) ions, have been synthesized as their potassium salts, where the amino acids are glycine, β-alanine, γ-aminobutyric acid, sarcosine, L-alanine, L-serine, L-valine and L-proline. The geometrical isomers have been separated by ion-exchange column chromatography and their structures determined on the basis of their absorption spectra and proton magnetic resonance spectra. Stereoselectivity about the formation of the trans and cis isomers was found. The circular dichroism of the complexes containing optically active amino acidato ligands has been measured and discussed in relation to so-called vicinal contribution by the optically active ligands.
  • Hideo Sato, Ryokichi Tarao, Hiromi Higashi
    1969 Volume 42 Issue 6 Pages 1588-1595
    Published: 1969
    Released: March 27, 2006
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    The infrared and proton nuclear magnetic resonance spectra of the solutions of diethylaluminum 2-aminoethoxide (AlEt2OCH2CH2NH2)2 and related compounds were measured. The infrared frequencies and intensities of the NH2 stretching, scissors, and rocking vibration bands, and the NMR internal chemical shifts of the ethyl groups attached to the aluminum atom were compared with the corresponding data of suitable model compounds. It was concluded by taking the results of these experiments into consideration that (AlEt2OCH2CH2NH2)2 was represented by the structural formula I with two Al←NH2 coordination bonds. Similarly, most of the related compounds studied were reasonably represented by the formulas with two Al←NRR′ coordination bonds, while (AlEt2OCH2CH2N(C6H11)2)2 was assumed to be represented by formula III with two Al←O coordination bonds, exceptionally.
  • Mutsuo Kodama, Katsumi Miyamoto
    1969 Volume 42 Issue 6 Pages 1596-1600
    Published: 1969
    Released: March 27, 2006
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    The addition of ammonia produces a remarkable change in the visible absorption spectra of copper(II)- and nickel(II)-aminopolycarboxylate chelates. This can be ascribed to the formation of a mixed ligand chelate involving ammonia and the aminopolycarboxylate anion. On the basis of the change in the absorbance of copper(II)- and nickel(II)-aminopolycarboxylate chelates, the solution equilibria between ammonia and these aminopolycarboxylate chelates were investigated. Copper(II) and nickel(II) chelates of ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)-ethylenediamine-N,N′,N′-triacetic acid (EDTA-OH), ethylenediaminetetrapropionic acid (EDTP), cyclohexanediaminetetraacetic acid (CyDTA), and diethylenetriaminepentaacetic acid (DTPA) were found to form mixed ligand chelates with a composition of M(NH3)Z2−n. From the intercept of the linear relation between log(AYA)⁄(AAM) and log[NH3]f, the equilibrium constant, KNH3, defined as KNH3=[M(NH3)Z2−n]⁄[MZ2−n]·[NH3]f, was determined.
  • Akifumi Yamada, Nobuyuki Tanaka
    1969 Volume 42 Issue 6 Pages 1600-1603
    Published: 1969
    Released: March 27, 2006
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    Kinetic parameters of the electrode reaction of ethylenediaminetetraacetatoaquochromate-(III)/ethylenediaminetetraacetatoaquochromate(II) at the dropping mercury electrode have been determined by the potentiostatic method in sodium chloride solutions of ionic strength 0.5 containing 0.1 M acetate buffer. The measured standard rate constant (ks)ms is 2.1×10−1cm sec−1 and the measured transfer coefficients (αc)ms and (αa)ms are 0.58 for the cathodic and 0.39 for the anodic process. The correction for the effect of the electrical double layer has been made on these parameters. The values obtained are: (ks)corrc=1.7×10 cm sec−1, (αc)corr=0.54 and (αa)corr=0.43. The standard potential −1.220 V vs. SCE determined by the potentiostatic method is compared with −1.218 V vs. SCE obtained by the measurement of the equilibrium potential. These values are in good agreement within the experimental error.
  • Jo Itakura, Hisao Tanaka, Hiroo Ito
    1969 Volume 42 Issue 6 Pages 1604-1608
    Published: 1969
    Released: March 27, 2006
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    The oxidation of eight- and twelve-membered cyclic olefins by H2O2 was carried out in various alcohols using some metal oxides as catalysts. In contrast to the case of cyclohexene and norbornene, which can be hydroxylated, the oxidation of 1,5,9-cyclododecatriene, cyclododecene, 1,3- and 1,5-cyclooctadiene and cyclooctene with H2O2 in the presence of selenium dioxide resulted in selective formation of the corresponding monoepoxides. The following rate equation was obtained with cyclooctene (COE) in isopropanol:
    −d[H2O2]⁄dt=k3′[SeO2][H2O2]+k3″[SeO2][H2O2][COE].
  • Kazuo Suzuki, Masahiro Minabe, Minoru Fujimoto, Noboru Nohara
    1969 Volume 42 Issue 6 Pages 1609-1617
    Published: 1969
    Released: March 27, 2006
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    A normal compound, 2′,7′-dibromotribiphenylenepropane (IV), and an abnormal compound, 2′,7′,2″,7″-tetrabromotribiphenylenepropane (VI), were obtained by the Michael addition of 9,9′-bifluorenylidene (I) and 2,7-dibromofluorene (III). In addition, another normal compound, 2,7,2′,7′-tetrabromotribiphenylenepropane (VIII) and three abnormal compound, IV, VI, and tribiphenylenepropane (VII), were isolated by the Michael addition of 2,7,2′,7′-tetrabromo-9,9′-bifluorenylidene (IX) and fluorene (II). In both cases, the normal compounds were obtained in the presence of sodium ethoxide in ethanol. The abnormal compounds might be formed by the further condensation of 2,7-dibromo-9,9′-bifluorenylidene (V) and III or II in the presence of alkali. The related compounds, 2,7-dibromotribiphenylenepropane (X), IV, VI, VIII, and 2,7,2′,7′,2″,7″-hexabromotribiphenylenepropane, were synthesized by the reaction of substituted 9-fluorenyllithium and substituted 9-bromo-9,9′-bifluorenyl in an absolute xylene solution. The thermal decomposition of X and VIII afforded bromosubstituted or nonbromosubstituted-9,9′-bifluorenylidenes, 9,9′-bifluorenyls, fluorenones, and fluorenes. The ethanolysis of 2,7-dibromo-9′-hydroxy-9,9′-bifluorenyl gave fluorenone and III.
  • Tadashi Sasaki, Shoji Eguchi, Takeshi Toru
    1969 Volume 42 Issue 6 Pages 1617-1621
    Published: 1969
    Released: March 27, 2006
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    Preparation of 1-adamantyl and adamantane-1-carbonyl derivatives having benzimidazole, 1,3,5-oxadiazole, oxazoline-2, quinoxaline, 2-aminothiazole, thiazolone, 2-methylthiazole, 1,2,3-thiadiazole, pyrazole or pyrazoline ring is described.
  • Shigeru Oae, Yong He Khim
    1969 Volume 42 Issue 6 Pages 1622-1627
    Published: 1969
    Released: March 27, 2006
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    o-, m-, and p-Chlorophenyldiphenylsulfonium halides were prepared and subjected to the alkaline ethanolysis in order to compare the activating effects of o-, m-, and p-diphenylsulfonio groups with those of o-, m-, and p-phenylsulfonyl and nitro-groups. The diarylsulfonio group at either ortho or para position was found to facilitate the nucleophilic substitution of aryl chloride powerfully. While the effect of diarylsulfonio group was not only substantially larger than that of phenylsulfonyl group, but also exceeding even that of nitro group. Meanwhile, with ethoxide ion in ethanol the alkaline decomposition reaction, presumed to be initiated by the attack of ethoxide on the sulfur atom of chlorophenyldiphenylsulfonium halide, occurred competitively along with the SN reaction, but the rate of the SN reaction of p-chlorophenyldiphenylsulfonium perchlorate was found to be about 9 times larger than that of the decomposition reaction. Substitution of a methyl group at ortho to diphenylsulfonio, phenylsulfonyl and -sulfinyl groups did change very little the rates of the ethanolyses of the corresponding p-substituted chlorobenzenes, suggesting that essentially there is no or little steric inhibition for the 3d-orbital resonance with either sulfonio, sulfinyl, or sulfonyl group in the SN reaction of these compounds.
  • Tsutomu Kagiya, Tomizo Kondo, Kenichi Fukui
    1969 Volume 42 Issue 6 Pages 1628-1633
    Published: 1969
    Released: March 27, 2006
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    The effect of the solvent on the copolymerization of N-phenylethylenimine with β-propiolactone has been studied quantitatively. The copolymerization rates for the various solvents used increase in the order: diethyl ether > toluene < carbon tetrachloride < methyl acetate < N,N-dimethylacetamide < anisole < dioxane < acetone < ethylene dichloride < acetonitrile < acetophenone < nitrobenzene < dimethyl sulfoxide < nitroethane. The rates in solvents with high dielectric constants are much larger than those in solvents with low dielectric constants. However, in the case of solvents with similar dielectric constants, the rates decrease with an increase in the nucleophilicity of the solvent; moreover, the dependency of the copolymerization rate on the nucleophilicity of the solvents is much larger in the solvents with high dielectric constants than in those with low dielectric constants. The rate of the consumption of N-phenylethylenimine is markedly affected by the nucleophilicity of the solvents in solvents with high dielectric constants, but it is little affected in solvents with low dielectric constants. Although there is no effect of the nucleophilicity of the solvents on the consumption rate of β-propiolactone, the rate of the consumption of β-propiolactone varies with the electrophilicity of the solvent in solvents with high dielectric constants. On the other hand, the β-propiolactone content in the copolymer increases in proportion to the nucleophilicity of the solvents with high dielectric constants, whereas the β-propiolactone content in solvents with low dielectric constants is almost constant regardless of the electric nature of the solvents.
  • Tsutomu Kagiya, Tomizo Kondo, Kenichi Fukui
    1969 Volume 42 Issue 6 Pages 1634-1640
    Published: 1969
    Released: March 27, 2006
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    The effect of the binary solvent system on the copolymerization of N-phenylethylenimine with β-propiolactone has been studied quantitatively. The copolymerization was carried out in three kinds of binary solvent systems, each consisting of components with similar dielectric constants (ε) and with very different nucleophilicities: (1) the nitrobenzene - N,N-dimethylacetamide system, ε\fallingdotseq36, (2) the ethylene dichlorice - tetrahydrofuran system, ε\fallingdotseq10, (3) the toluene-anisole system, ε\fallingdotseq3. In the binary solvent system with the highest dielectric constant, the copolymerization rate decreased with an increase in the content of the nucleophilic solvent. In the nitrobenzene -N,N-dimethylacetamide system, the copolymerization rate markedly decreased upon the addition of a small amount of N,N-dimethylacetamide in nitrobenzene. On the other hand, in the ethylene dichloride - tetrahydrofuran binary solvent system, with a lower dielectric constant than the nitrobenzene and N,N-dimethylacetamide system, the rates decreased in proportion to the tetrahydrofuran content. The β-propiolactone content in the copolymer increased with the amount of the larger nucleophilic solvents, and the dependency of the copolymer composition on the nucleophilicity of the solvents was much larger in the binary solvents with high dielectric constants than in the binary solvents with low dielectric constants. In the toluene - anisole system, which has a very low dielectric constant, the copolymerization rate and the composition of the copolymer were almost constant, independent of the composition of the solvents.
  • Keisuke Murayama, Syoji Morimura, Takao Yoshioka
    1969 Volume 42 Issue 6 Pages 1640-1643
    Published: 1969
    Released: March 27, 2006
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    We have isolated coupled products of such stable free radicals as 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (II), cyclohexane-1-spiro-2′-(4′-oxoimidazolidine-l′-oxyl)-5′-spiro-l″-cyclohexane (IV) and 2,2,6,6-tetramethyl-4-oxopiperidine-1-thiyl derived from bis-[2,2,6,6-tetramethyl-4-oxopiperidyl-(1)]disulfide (VII) with a C-radical derived from α,α′-azo-bis(isobutyronitrile). The reactive site in these stable free radicals was studied from the structure of the coupled products. The homolysis of the disulfide (VII) appeared to be accelerated by an attack of the C-radical, 1-methyl-1-cyanoethyl. The NMR spectra of the products suggested a slow inversion of the nitrogen atom in piperidine derivatives.
  • Heimei Yuki, Yoshio Okamoto
    1969 Volume 42 Issue 6 Pages 1644-1649
    Published: 1969
    Released: March 27, 2006
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    Anionic copolymerization of isoprene (M1) and 1,1-diphenylethylene (M2) was carried out in tetrahydrofuran (THF), dioxane, benzene, and n-heptane by using n-butyllithium (n-BuLi), Na-naphthalene, Na- and K-dispersions as initiators. An alternating copolymer was obtained in the copolymerization in THF, which proceeded without a chain transfer and a termination. Monomer reactivity ratios, r1 obtained by assuming the rate constant k22=0, were 0.12 (Li+), 0.11 (Na+), and 0.11 (K+) in THF at 0°C. The r1 value in benzene at 40°C, however, was affected by the counter ion as follows: 37 (Li+), 0.38 (Na+), and 0.05 (K+). With Li+ counter ion the values were 0.50 in dioxane at 30°C and 29 in n-heptane at 40°C. The order of rate constants in the copolymerization in THF with n-BuLi at 0°C, was k12>k11>k21, the last of which was 2.64×10−3l/mol sec.
  • Kenji Fukui, Mitsuru Nakayama, Tokunaru Horie
    1969 Volume 42 Issue 6 Pages 1649-1652
    Published: 1969
    Released: March 27, 2006
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    By using the method of Allan-Robinson’s flavone synthesis, the condensation of 3,ω-dimethoxy-2,1,6-trihydroxyacetophenone with 3,4-dibenzyloxybenzoic anhydride gave a mixture of 3,6- and 3,8-dimethoxy-3′,4′-dibenzyloxy-5,7-dihydroxyflavone (X and XI). The catalytic debenzylation of the above flavones then gave axillarin (I) and 3,8-dimethoxy-5,7,3′,4′-tetra-hydroxyflavone (IV) respectively. Axillarin 7-O-methyl ether(III) was prepared by the partial methylation of X, followed by catalytic debenzylation.
  • Hideo Baba, Isaburo Hori, Toshio Hayashi, Hiroshi Midorikawa
    1969 Volume 42 Issue 6 Pages 1653-1659
    Published: 1969
    Released: March 27, 2006
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    α-Cyano-β-methoxy-β-alkyl (Me, Et, n-Pr, n-Bu, n-Am, and i-Bu)-acrylic esters (I) react with hydrazine to give β-hydrazino intermediates. The hydrazino group of these intermediates is cyclized preferentially between its terminal NH2 and the cyano group in a neutral or acidic medium to give 5-aminopyrazole derivatives, and preferentially between the terminal NH2 and the ester group in the presence of a base to give 5-pyrazolone derivatives. When the β-alkyl of I is isopropyl, t-butyl], etc., I affords only the 5-pyrazolone derivatives in the reaction with hydrazine. The reactions of I with hydroxylamine gave 5-aminoisoxazole derivatives, but in the case of the β-t-butyl derivative of I they gave 5-aminoisoxazole accompanied by the 5-isoxazolone derivative.
  • Yasuhiko Kondo, Niichiro Tokura
    1969 Volume 42 Issue 6 Pages 1660-1663
    Published: 1969
    Released: March 27, 2006
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    The expression which relates the activation entropies of the reactions measured in various solvents with the products of the coefficients of thermal expansion and the molar volumes of the respective solvents has been derived based on the concepts of the electrostriction theory. For three Menschutkin reactions and one acylation reaction linear correlations to be expected from the above expression have been found between the activation entropies and the products of the coefficients of thermal expansion and the molar volumes of the solvents. Moreover, the interrelation between the activation volumes and the activation entropies has been discussed based on this model.
  • Yoshinobu Takegami, Toru Ueno, Takao Fujii
    1969 Volume 42 Issue 6 Pages 1663-1667
    Published: 1969
    Released: March 27, 2006
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    Catalysts composed of anhydrous iron(III) chloride, cobalt(II) chloride, or nickel(II) chloride plus triethylaluminum have been used for the hydrogenation of olefin. The catalytic activity has changed with the Al(C2H5)3/MCln ratio. The optimum ratios for the hydrogenation of styrene have been found to be 1–7 for the iron catalyst, 0.2–1 for the cobalt catalyst, and 0.3–2 for the nickel catalyst. Cyclohexane has been used satisfactorily as a solvent. Tetrahydrofuran could be used for the nickel catalyst, but its presence was unfavorable for the iron and cobalt catalysts. The gas evolved in the reaction of the transition metal chlorides with triethylaluminum has been found to be essentially ethane, and sluggish gas absorption was observed when the atmosphere was switched to hydrogen. Ethylbenzene was formed in the treatment of the catalyst with styrene under nitrogen; the amount increased considerably if the catalyst was pre-treated with hydrogen. Ethane was formed in the hydrogen-treatment of the reaction mixture of nickel chloride and triethylaluminum. On the basis of these results, it has been assumed that metal hydride has been formed by the hydrogenolysis of metal - ethyl bonds.
  • Takashi Maeda, Mitsuru Kimoto (née Katsuhara), Shigeru Wakahara ...
    1969 Volume 42 Issue 6 Pages 1668-1678
    Published: 1969
    Released: March 27, 2006
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    The acid-catalyzed benzylidenation of L-sorbose (I) was studied. The reaction by Reichstein’s procedure gave a mixture of two diastereomeric 2,3:4,6-di-O-benzylidene-α-L-sorbofuranoses (III and IV), which were then successfully separated by preparative thin-layer chromatography. The use of slightly acidic conditions yielded l,3:4,6-di-O-benzylidene-β-L-sorbofuranose (XI), l,2:4,6-di-O-benzylidene-α- (XVII and XVIII) and-β-L-sorbofuranoses (XIX and XX), 1,2-O-benzylidene-α-L-sorbopyranoses (XXI and XXII), and 1,3-O-benzylidene-L-sorbose (XXIII). The absolute configurations at the acetal center of the five-membered benzylidene rings were assigned. A reaction sequence (I→(XXI, XXII\ ightleftarrowsXXIII)→XI→IV→III) comparable with that of the ethylidenation of I was established.
  • Hisao Nakata, Akira Tatematsu
    1969 Volume 42 Issue 6 Pages 1678-1683
    Published: 1969
    Released: March 27, 2006
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    In order to examine a possibility of keto-enol tautomerism in molecular and fragment ions, diethyl di-n-butylmalonate (Ia), methyl 2-n-butylhexanoate (IIa), and 2,2-di-n-propyl-5,5-dimethyl-1,3-cyclohexanedione (IIIa) were synthesized and their mass spectra were compared with those of respective mono-alkyl derivatives, Ib, IIb, and IIIb. The first step of the fragmentation of each dialkyl compounds is the cleavage of one of the alkyl side chains by McLafferty rearrangement to give an enol fragment ion (E). Comparisons of the behavior of this enol fragment ion with that of the corresponding molecular ion (K) of mono-alkyl derivatives indicate that the keto and enol forms of these compounds exhibited entirely different fragmentation patterns. Thus, the enol fragment ion of m/e 216 from Ia loses C3H7· through the allylic cleavage of an enol double bond to give an abundant m/e 173 peak, while the keto ion of m/e 216 from Ib loses C4H8 to afford a strong m/e 160 peak. In a similar manner, the enol fragment ion of m/e 130 from IIa gives an intense peak at m/e 87, and the keto ion of m/e 130 from IIb yields an ion at m/e 74. In the spectrum of IIIa, a peak at m/e 140 that is observed in the IIIb spectrum did not appear. These results clearly suggest that no keto-enol tautomerism takes place in these ions in a mass spectrometer.
  • Teruo Ueda, Kan Inukai, Hiroshige Muramatsu
    1969 Volume 42 Issue 6 Pages 1684-1687
    Published: 1969
    Released: March 27, 2006
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    The radiation-induced addition reactions of dialkyl phosphites to polyfluorocyclobutenes, such as perfluoro-, 1,2-dichlorotetrafluoro-, 1-chloro-2,3,3,4,4-pentafluoro-, 1,3,3,4,4-pentafluoro- and 1-chloro-3,3,4,4-tetrafluorocyclobutenes were carried out. In general, the corresponding dehydrohalogenated 1 : 1 adducts, polyfluorocyclobutenylphosphonates, were obtained as the main products instead of the expected 1 : 1 adducts. The direction of attack of the phosphonyl radical on the unsymmetrical double bond and reaction mechanism were discussed.
  • Tsutomu Kagiya, Masatsune Kondo, K\={o}z\={o} Narita, Kenichi Fukui
    1969 Volume 42 Issue 6 Pages 1688-1693
    Published: 1969
    Released: March 27, 2006
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    The cause of the polymerizability of formaldehyde in liquid carbon dioxide was studied in connection with the preparation conditions of the monomer. A liquid carbon dioxide solution of the monomer was prepared by two different methods, by means of the pyrolysis of α-polyoxymethylene and by means of that of the hemiformal of polyethylene glycol, under a carbon dioxide stream. By adding various sodium salts to the pyrolysis system of α-polyoxymethylene, the polymerization rate, without the addition of any catalyst, of the monomer thus obtained was found to decrease with an increase in the pKa value of the conjugated acid of the salt. The polymerization rate also decreased with the amount of sodium carbonate added. The hemiformal of polyethylene glycol was prepared by bubbling the gas evolved by the pyrolysis of paraformaldehyde into polyethylene glycol. The amount of acid present in the hemiformal thus obtained increased linearly with the pyrolysis time. The polymerization rate of the monomer obtained by the pyrolysis of the hemiformal increased in proportion to the acid content in the hemiformal. On the basis of these results, the initiation mechanism in the polymerization of formaldehyde without any additional initiator in a liquid carbon dioxide solution was discussed.
  • Kenji Fukui, Mitsuru Nakayama, Teruo Harano
    1969 Volume 42 Issue 6 Pages 1693-1697
    Published: 1969
    Released: March 27, 2006
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    4′,5′-Dimethoxy-2′-hydroxyfurano[3″,2″:6,7]isoflavone was obtained from isoelliptol isoflavone by selective demethylation with boron tribromide. The treatment of the 2′-hydroxyisoflavone with sodium borohydride in absolute alcohol - tetrahydrofuran afforded 8,9-dimethoxyfurano[3′,2′:2,3]pterocarpan. 8,9-Dimethoxyfurano[2′,3′:3,4]pterocarpan was prepared from elliptol isoflavone by a similar procedure.
  • Koshin Miyazaki
    1969 Volume 42 Issue 6 Pages 1697-1702
    Published: 1969
    Released: March 27, 2006
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    1,1-Disubstituted-3-(4-chlorophenyl)-3-(phenoxythiocarbonyl)-2-thioureas of the formula R,R′N–C1(=S)–N(p-Cl–C6H4–)–C′(=S)–OC6H5 (II), when kept at an elevated temperature without any solvent, decomposed into the corresponding thionocarbamates of the formula R,R′N–C(=S)–OC6H5 (III), while p-chlorophenyl isothiocyanate was eliminated. A carbon-14-labeling experiment showed that the decomposition proceeded only through the following path:
    II→R,R′N–C2(=S)–OC6H5+p-Cl–C6H4–N=C1=S
    Kinetic studies of the various II showed that the decompositions were strictly first order. The rate constant at 175°C increased in the order: R,R′=(CH3)2>(C2H5)2>CH3,4-methylbenzyl\gtrsim (n-C3H7)2>CH3, benzyl>CH3, 4-chlorobenzyl. Neither the products nor the rate of the decomposition reaction was influenced by the presence of a radical scavenger. Furthermore, a crossover decomposition reaction did not give any crossover products. On the basis of these results, a possible intramolecular mechanism of the decomposition involving a four-membered cyclic intermediate structure was proposed.
  • Akira Kasahara, Keiko Tanaka, Taeko Izumi
    1969 Volume 42 Issue 6 Pages 1702-1704
    Published: 1969
    Released: March 27, 2006
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    Sodium tetrachloropalladate(II) reacts with 2-vinylpyridine in methanol, ethanol, or isopropyl alcohol, to give, respectively, di-μ-chloro-bis[2-methoxy-2-(α-pyridyl)ethyl]dipalladium(II), di-μ-chloro-bis[2-ethoxy-2-(α-pyridyl)-ethyl]dipalladium(II), and di-μ-chloro-bis[2-isopropoxy-2-(α-pyridyl)ethyl]-dipalladium(II). The reaction of potassium tetrachloroplatinate(II) with 2-vinylpyridine in methanol or ethanol affords, respectively, di-μ-chloro-bis[2-methoxy-2-(α-pyridyl)ethyl]diplatinum(II) and di-μ-chloro-bis[2-ethoxy-2-(α-pyridyl)ethyl]diplatinum(II). The structures of these complexes containing the covalent metal - carbon bonding have been confirmed by a study of their absorptions and of the NMR spectra.
  • Toshikazu Nagai, Hironobu Abe, Niichiro Tokura
    1969 Volume 42 Issue 6 Pages 1705-1708
    Published: 1969
    Released: March 27, 2006
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    The reason for the rate-enhancing effect of liquid sulfur dioxide on the rate of the benzoylation of methanol has been studied. The observation of the NMR spectra revealed that the amount of the hydrogen-bonded methanol is decreased (but not completely eliminated) by sulfur dioxide in the liquid SO2-CCl4 system. The existence of a correlation between the rates of esterification and the dissociation of the associated alcohol accounts for the role of the sulfur dioxide as the agent for the dissociation of the methanol-hydrogen bonding during the esterification.
  • Yasuhiko Kondo, Toshiharu Kusaka, Niichiro Tokura
    1969 Volume 42 Issue 6 Pages 1708-1712
    Published: 1969
    Released: March 27, 2006
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    The rate constants of the Menschutkin reaction between methyl iodide and pyridine, N,N-dimethylaniline, 2,6-dimethylpyridine, and N,N-dimethyl-o-toluidine have been measured in a liq. SO2-nitrobenzene mixture. These results have then been analyzed by the procedure described in a previous paper. The findings regarding the reactions of unsubstituted amines with methyl iodide have been explained theoretically by taking into account the specific solvation of amines by liq. SO2 and that of an activated complex by a nitrobenzene solvent, whereas the behavior of the rate constants in the reactions of o-substituted amines in mixed solvents can be explained by assuming the specific solvation of an activated complex by liq. SO2 only. In conformity with the above results and the difference in the effect of an o-methyl group on the reaction rates between liq. SO2 and a nitrobenzene solvent, the mutual relation of the activation free energies of these reactions has been discussed.
  • Masatsune Kainosho, Asao Nakamura, Masamichi Tsuboi
    1969 Volume 42 Issue 6 Pages 1713-1718
    Published: 1969
    Released: March 27, 2006
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    Proton magnetic resonance spectra for eleven compounds with the POCH system have been examined. They are three 4-phenyl-2,2-disubstituted(X,Y)-1,3,2-dioxaphosphorinanes where X=Cl, Y=O (I); X=Cl, Y=S (II); and X=OK+, Y=O (III); four 5,5-dimethyl-2,2-disubstituted (X,Y)-1,3,2-dioxaphosphorinanes where X=Cl, Y=O (IV); X=Br, Y=O (V); X=Cl, Y=S (VI); and X=OH, Y=O (VII); and four dimethyl phosphates, Y=P(-X)-(-OCH3)2, where X=Cl, Y=O (VIII); X=Br, Y=O (IX); X=Cl, Y=S(X); and X=O\frac12Ba2+, Y=O (XI). It has been found that the 1,3,2-dioxaphosphorinane ring in each of I–VIII is virtually fixed in a chair form in the solution, and there is no appreciable ring inversion as confirmed by NMR spectra. The phosphorus-proton coupling constant of the POCH system with the gauche relation (Jg) and that with the trans relation (Jt) were determined in each of these compounds (I–VII). The \frac23Jg+\frac13Jt values calculated from the determined Jg and Jt values are always smaller than the \frac23Jg+\frac13Jt values observed for the corresponding acyclic compounds (VIII–XI). This difference was explained in terms of a slight flattening of 1,3,2-dioxaphosphorinane ring from the ideal chair conformation.
  • Hiroaki Yanagisawa, Mitsuhiro Kinoshita, Sumio Umezawa
    1969 Volume 42 Issue 6 Pages 1719-1725
    Published: 1969
    Released: March 27, 2006
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    Cyclization of D′-methoxy-diglycolaldehyde, prepared by periodate cleavage of methyl β-L-arabinopyranoside, with ethyl nitroacetate gave a mixture of stereoisomers of cyclic α-nitro ester, i.e. methyl (+)-3-deoxy-3-C-ethoxycarbonyl-3-nitropentopyranoside. Catalytic reduction of the cyclic α-nitro ester afforded an isomeric mixture of cyclic α-amino esters, from which, on column chromatography, there could be isolated four diastereoisomers of methyl (+)-3-amino-3-deoxy-3-C-ethoxycarbonylpentopyranoside. Hydrolysis of each diastereoisomer gave the corresponding cyclic (+)-α-amino acid having a skeleton of pentopyranoside. The stereochemistry of the isomeric amino acids was studied by NMR spectroscopy and chemical degradation. On the other hand, three enantiomeric cyclic (−)-α-amino acids were also obtained from methyl β-D-xylopyranoside by the analogous route as that from methyl β-L-arabinopyranoside.
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