Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 11
Showing 1-50 articles out of 101 articles from the selected issue
  • Masashi Matsuo, Yasukazu Saito
    1971 Volume 44 Issue 11 Pages 2889-2893
    Published: 1971
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The redox decomposition process of hydroxymercurated propylene in aqueous solution yielding acetone has been followed by time-sequential NMR spectroscopy in situ. No reaction intermediates and reaction products other than acetone were observed. Stoichiometric relationship holds between the reactant and the product during the reaction, which was verified by NMR spectra. The reaction rate was confirmed to be of first order with respect to mercurial. Although the rate was accelerated at higher acidity in solution, a similar rate enhancement took place by addition of neutral salts. At a certain ionic strength, no close linear correlation between the apparent rate constants and proton concentration was observed. In contrast, excellent linear dependence was obtained by the thermodynamic activities of the added electrolytes including acid. Since the apparent rate constant was independent of the concentration of free mercuric ion, a monomolecular mechanism is proposed. Taking into account the rate dependence upon added electrolytes, the redox decomposition of the hydroxymercurated olefins to give carbonyl compounds seems to proceed only when an aquo ligand is removed from the carbon-bonded mercuric ion.
  • Takashi Kotoyori, Makoto Takahasi, Akira Ichinose
    1971 Volume 44 Issue 11 Pages 2893-2899
    Published: 1971
    Released: March 27, 2006
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    Reaction of methanol with accelerated rare gas ions was studied. The yields of the reaction products, H2, CO, CH4, HCHO, and ethylene glycol, were determined, varying the initial kinetic energy of ion (2–6 kV), ionic species, (Ar, Xe, and Kr), and pressure of methanol ((2–14)×10−3 Torr). No appreciable effect on the product yields was observed by adding carbon tetrachloride as electron scavenger or propylene as radical scavenger. The product yields are found to be linear against In Ei, (Ei is initial kinetic energy of ions). Although the detailed reaction mechanism is left for future investigation, the reaction seems to be interpreted in terms of billiard model, momentum of ion being transferred directly to a local part of the target molecule at the contact time.
  • Yoshinori Hasegawa
    1971 Volume 44 Issue 11 Pages 2900-2903
    Published: 1971
    Released: March 27, 2006
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    The near ultraviolet absorption spectrum of pyridine-d5 vapor due to n–π* transition was measured and analyzed. The origin is at 34951 cm−1 and higher than that of pyridine-h5 by 182 cm−1. The ground-state frequencies 582 and 1019 cm−1 and their counterparts of 511 and 953 cm−1 in the upper state dominate the progressions in the spectrum. Besides the above frequencies, several active frequencies were obtained.
  • Tatsuya Sekine, Yasuaki Koike, Y\={u} Komatsu
    1971 Volume 44 Issue 11 Pages 2903-2911
    Published: 1971
    Released: March 27, 2006
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    The rate of extraction of beryllium ions from aqueous 4.0M or 0.1M sodium perchlorate-chloride or -nitrate ionic media into carbon tetrachloride or MIBK (methyl isobutyl keton) as a chelate complex with TTA (thenoyltrifluoroacetone) has been determined at 25°C. The rate of extraction in the carbon tetrachloride system is first-order with respect both to the beryllium ion and the dissociated TTA anion in the aqueous phase. The rate constant for this reaction is about 2×104M2min−1. The rates in these systems are not influenced by the replacement of perchlorate ions by nitrate or chloride ions in the ionic media when the ionic concentration is kept constant. On the other hand, it was found that three extraction reactions take place in the MIBK systems. The rate of these extractions is in all cases first-order with respect both to the beryllium ion and the dissociated TTA anion, but is zeroth-, first, or second-order with respect to the perchlorate ions in the aqueous phase. Because of this, the extraction is much faster when the perchlorate concentration is larger; for example, when the concentration of the TTA anion is kept constant, the extraction from a 4.0M sodium perchlorate solution is about 200 times faster than that from the 4.0M sodium chloride solution. From these experimental results, the following conclusions were reached. In the carbon tetrachloride system, the beryllium ion first forms the TTA chelate in the aqueous phase, and then the complex is extracted into the organic phase. The rate-determining step is the 1: 1 complex formation in the aqueous phase. In the MIBK system, on the other hand, the formation of the TTA complex in the aqueous phase, followed by its extraction into the organic phase (zeroth-order reaction with respect to the perchlorate ion), also occurs, but at the same time, the beryllium ion in the aqueous phase is first extracted into the organic phase as ion-pairs, such as BeCl(ClO4) or BeNO3(ClO4) and Be(ClO4)2 (first- and second-order reactions with respect to the perchlorate ions respectively), and the ion-pairs then react with the TTA anions in the organic phase. The enhancement of the rate of extraction by the perchlorate ions in the MIBK system seems to be explained by the overall effect of these extraction mechanisms.
  • Motoharu Shiba, Yasuaki Kawano, Suiichi Tomioka, Masumi Koishi, Tamots ...
    1971 Volume 44 Issue 11 Pages 2911-2915
    Published: 1971
    Released: March 27, 2006
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    Electrophoretic measurements were made on polyphthalamide microcapsules containing aqueous solution of bovine serum albumin and their membrane at various hydrogen ion concentrations. The microcapsules moved toward the anode at any pH, while the membrane migrated to the anode above pH 3.5 and to the cathode below this pH. These results were explained on the assumption that a fraction of albumin molecules is chemically incorporated into the microcapsule membrane through the microencapsulation and that the net electrical charge of the microcapsules is highly dependent on the charge of the outer surface of their membrane.
  • Shukichi Sakuraba, Ryoka Matsushima
    1971 Volume 44 Issue 11 Pages 2915-2918
    Published: 1971
    Released: March 27, 2006
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    The relative rates for uranyl fluorescence quenching by aliphatic alcohols (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and s-butyl alcohols) were measured under various conditions. The rates were increased in proportion to the perchloric acid concentration at pH <1, whereas the rates were smaller and nearly constant at the pH’s between 1–4; thus showing the involvement of both acid-dependent and acid-independent processes. Though the rates for both processes changed with the change in the alcohol structure (the polar substituent effect), the ratio of the two rate constants was nearly constant. The inhibitory effects of cupric ions (as a scavenger for the one-equivalent redox intermediates) suggested that the acid-dependent quenching process involves a two-equivalent redox or two consecutive one-equivalent redox steps between the same partners. The mechanisms of these quenching processes are discussed.
  • Tsutomu Seimiya, Kazuo Ohbu, Akio Nakamura, Tsunetaka Sasaki
    1971 Volume 44 Issue 11 Pages 2918-2921
    Published: 1971
    Released: March 27, 2006
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    The process of desorption of dodecanol monolayer into the aqueous sodium dodecyl sulfate (SDS) solutions of varying concentrations was studied by the surface tension measurement. The rate of desorption in its early stage obeyed the simple diffusion law and the plot of logarithms of surface pressure against the square root of time showed a linear relationship. The rate constant of desorption decreased slightly and linearly with an increasing concentration of SDS up to CMC. Beyond CMC it increased rapidly and linearly owing to the increase of dodecanol solubility due to the solubilization. Further, from these rate constants and the surface tension vs. concentration curve, the diffusion coefficient of dodecanol in water and in aqueous SDS solutions, its solubilization in aqueous SDS solution and the partition coefficient of dodecanol between water and SDS micelles were calculated. Critical micelle concentration of sodium dodecyl sulfate was also determined as a break point of desorption constant vs. concentration curve.
  • Masamichi Tsuboi, Seizo Takahashi, Shuichi Muraishi, Teruo Kajiura
    1971 Volume 44 Issue 11 Pages 2921-2925
    Published: 1971
    Released: March 27, 2006
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    The Ramam spectra of β-uridine-5′-phosphoric acid (UMP), its deuterated product, β-uridine-3′-β-uridine-5′-phosphoric acid (UpU), and polyribouridylic acid (poly U) have been observed in their aqueous solutions; and the Raman lines assignable to the phosphate group and to the base residue have been indicated. For UMP, the intensity ratio of a Raman line of the base residue versus that of the phosphate group was found to become greater on changing the exciting line from the 6328 Å line of a helium-neon laser to the 4880 Å line of an argon ion laser. This fact has been taken as indicating that a preresonance Raman effect takes place of the base residue with the effective absorption at 2600 Å.
  • Akimichi Yokozeki, Kozo Kuchitsu
    1971 Volume 44 Issue 11 Pages 2926-2930
    Published: 1971
    Released: March 27, 2006
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    The structure and the rotational isomerism of ethylenediamine have been investigated by means of gas electron diffraction. Evidence has been given for the presence of one conformer (gauche) in the vapor phase (at 50–120°C); the N–C–C–N dihedral angle measured from the cis position is 64·0±4°, and the fraction of any other isomer, if present, is estimated to be less than 5%. A theoretical prediction based on the SCF-CNDO/2 method has essentially accounted for this finding. The rg distances and the angles based on the ra structure determined by a least-squares analysis on molecular intensities, with estimated limits of error, are as follows: C–C=1.545±0.008 Å, C–N=1.469±0.004 Å, ∠C–C–N=110.2±0.7°, C–H=1.109±0.01 Å, ∠C–C–H=111·9±5°, and ∠H–C–H=112·7±8°.
  • Kazuo Sato, Atsuo Nishioka
    1971 Volume 44 Issue 11 Pages 2931-2935
    Published: 1971
    Released: March 27, 2006
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    The proton spin-lattice relaxation and the chemical shift were studied in N-methylacetamide (NMA) and N,N-dimethylacetamide (DMA) in p-dioxane and chloroform. In the p-dioxane solution, it has been found that the self-association of NMA does affect its spin-lattice relaxation, whereas the amide-solvent association does not affect it entirely. This was interpreted in terms of the lifetime of the inter-amide (\simeq10−11–10−12 sec) and the amide-solvent association (much shorter than 10−11–10−12 sec). On the other hand, the effect of the amidesolvent association on the spin-lattice relaxation is pronounced in chloroform, as is the effect of the self-association of NMA. The inter-amide interaction which leads the double-bond character of DMA to be more stable was not reflected distinctly in the concentration dependence of the spin-lattice relaxation times of DMA.
  • Hiroshi Fujimoto, Shinichi Yamabe, Kenichi Fukui
    1971 Volume 44 Issue 11 Pages 2936-2941
    Published: 1971
    Released: March 27, 2006
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    The wave functions of a system composed of two mutually-interacting molecules have been expressed in terms of configuration interaction wave functions. The electron configurations have been taken into account with respect to the states of adiabatic interaction, delocalization interaction, and polarization interaction. The electron populations in all of these states have been obtained separately. It has been demonstrated that the adiabatic interaction between two closed-shell molecules can not be the origin of the bond interchange in chemical reactions. The inclusion of charge-transferred states has been shown to be of great importance in explaining the formation of new bonds and the weakening of old bonds in the case of chemical interaction between two molecules. On the basis of the results of numerical calculations on some typical reaction models, the important role of the orbital overlapping interaction of the highest occupied molecular orbital and the lowest unoccupied molecular orbital has been pointed out.
  • Tatsuya Sekine, Naohiko Ihara
    1971 Volume 44 Issue 11 Pages 2942-2950
    Published: 1971
    Released: March 27, 2006
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    The distribution of copper(II) and zinc(II) chelates with three β-diketones, acetylacetone (AA), trifluoroacetylacetone (TFA), and hexafluoroacetylacetone (HFA) between carbon tetrachloride and aqueous sodium perchlorate solutions at 0.1M, 1M, and 3M has been determined at 25°C as a function of the concentration of the dissociated chelate anions. The stability constants for the metal chelates in the aqueous phase and the two phasedistribution constants for the uncharged complexes have been determined by a graphic analysis of the distribution data. The distribution was also measured when the carbon tetrachloride phase was added with tributylphosphate (TBP) or trioctylphosphine oxide (TOPO) and the adduct-formation constants of the uncharged chelate with these ligands have been determined by a graphic analysis of the increase in the distribution ratio as a function of the ligand concentration. The results are as follows: (i) Copper(II) forms first and second complexes with these chelating ligands in the aqueous phase, whereas zinc (II) forms the third complex (except with HFA) besides the first and the second ones; the complexes are more stable in the ligand order of AA>TFA>HFA. (ii) The stability constants of the copper(II) complexes are much higher than those of the corresponding zinc(II) complexes. (iii) The distribution constant of the uncharged copper(II) complex is higher than that of the corresponding zinc(II) complex. (iv) No remarkable relation has been found among the distribution constants of the chelating acid and those of the uncharged metal chelates. (v) The adducts of the metal chelates are more stable in the ligand order of HFA>TFA>AA. The zinc(II) complex forms more stable adducts than does the corresponding copper(II) complex, and TOPO forms more stable adducts than does TBP. (vi) Changes in the concentration of the background salt alter the stability constants of the metal chelates and the distribution constants of the uncharged chelate (salting-out); the effects are, however, very complicated. On the basis of these results, the distribution constants of the uncharged chelates were discussed from the standpoint of the interactions of the central metal ions in the complexes with the water molecules, and a qualitative relationship between these interactions and the stabilities of the adduct chelate complexes was pointed out.
  • Hiroshi Yoshida, Tetsuo Warashina
    1971 Volume 44 Issue 11 Pages 2950-2954
    Published: 1971
    Released: March 27, 2006
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    By observing electron spin resonance spectra during photolysis at room temperature, kinetic behaviors of short-lived free radicals are studied in photoreduction of benzophenone in alcohols, especially in ethanol, with and without sodium methoxide. In neutral solution, diphenylhydroxymethyl radicals and hydroxyethyl radicals are observed simultaneously. This is a firm evidence, obtained from ESR, of hydrogen abstraction of excited benzophenone from ethanol. Results indicate that (1) free radicals are the most efficiently generated by the light of ∼350 nm, (2) hydroxyethyl radicals transform into diphenylhydroxymethyl radicals if the concentration of benzophenone is high, and (3) the latter radicals disappear following the second order reaction. In the presence of sodium methoxide, diphenylhydroxymethyl radicals transform into benzophenone ketyl anions.
    Rate constants are determined, being 3×107 and ∼104 mole−1·1·sec−1 for the combination reaction between diphenylhydroxymethyl radicals and the proton transfer reaction from diphenylhydroxymethyl radical to methoxide ion, respectively.
  • Toshihiko Ishikawa, Seiichi Karino, Susumu Nagai, Noritake Yasuoka, No ...
    1971 Volume 44 Issue 11 Pages 2954-2959
    Published: 1971
    Released: March 27, 2006
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    The structure of 1,4-Bis(p-bromophenoxy) butane has been determined by means of a single-crystal X-ray analysis. The compound crystallizes in the monoclinic space group Cc, with four molecules per unit cell: a=13.426, b=15.249, c=7.650 Å, and β=89.39°. The structure has been solved by the heavy-atom method. The final discrepancy index is 0.068 for 970 non-zero reflections. The conformation of the methylene chain in the –O(CH2)4O– group is gauche-trans-gauche, with internal rotation angles of 61.0, 181.0, and 55.2° respectively.
  • Yoshiharu Matsuda, Akira Shono, Chiaki Iwakura, Yoshiki Ohshiro, Toshi ...
    1971 Volume 44 Issue 11 Pages 2960-2963
    Published: 1971
    Released: March 27, 2006
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    The anodic oxidation of aniline in an aqueous alkaline solution was studied. The anode materials were Ni, C, Pt, and Pb. An organic deposit (film) was formed on the anodes. The reaction mechanism was estimated through electrochemical measurements, chemical analysis, thin-layer chromatography, and UV, NMR, and IR spectrometries. The de-electronation of lone-pair electrons of the N atom in an aniline molecule caused the radical cation to be produced, (Remark: Graphics omitted.), and this process was the rate-determining step. Some of the radical cations were found to couple together to produce azo-benzene via hydrazobenzene. The other radical cations led to p-amino diphenylamine by head-to-tail coupling; this product was de-electronated again to give the polymer with a quinoid structure.
  • Kazuhiko Ichikawa, Mitsuo Shimoji
    1971 Volume 44 Issue 11 Pages 2964-2967
    Published: 1971
    Released: March 27, 2006
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    The initial and steady-state potentials of thermocells of the liquid I2+Te system were measured at temperatures 250–600°C. Cells with a vapor path were used, together with those in which a vapor transport was forbidden. The difference due to these types of cells was found in the values of not the initial thermoelectric powers but the steady-state ones for only solutions with low Te compositions. In the I2-rich region, the mechanism is discussed by using the model of charge-transfer due to I3 as in the case of conductivities and absorption spectra. The thermoelectric data in both the Te-rich and intermediate composition regions suggest that electronic contributions are highly predominant and a transition to delocalized states continuously appears with increasing Te concentration. Some experiments were carried out in order to examine the formation of concentration gradient due to the thermal effect in low Te compositions.
  • Masuo Aizawa, Shuichi Suzuki
    1971 Volume 44 Issue 11 Pages 2967-2971
    Published: 1971
    Released: March 27, 2006
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    The dilatometric properties of W1 W2, and W3, which were proposed by the present authors, for the classification of water in macromolecular gels, are studied over the range from −30 to 60°C. From the results of the thermal expansion of agarose gels and Sephadex (cross-linked dextrans), higher water contents of gel were found to show an extremely sharp volume change at 0°C; on the contrary, lower water contents of gel exhibited no anomalous change in the specific volume in the range from −30 to 0°C, and a gradual decrease in the specific volume was detected with an increase in the temperature in the range from −20 to 0°C for medium water contents of the gel, though the gel was expected to increase in its volume in that temperature range. Thus, the new classification for the states of water in macromolecular gels was shown to be reasonable, at the same time, the transition temperatures of W1 W2, and W3 were evaluated on the basis of the above results.
    The thermal expansion of water in macromolecular gels, even of W1 was found to be extremely depressed by the polymers of such gels.
  • Tsuguo Yamaoka, Saburo Nagakura
    1971 Volume 44 Issue 11 Pages 2971-2975
    Published: 1971
    Released: March 27, 2006
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    The reactions of various aliphatic amines with p-benzoquinone and its chloro-derivatives were studied by detecting reaction intermediates by means of the rapid scan spectrophotometric method. A detailed kinetic study on the reaction intermediate and the final product was made for the system including n-butylamine and chloranil in ethanol; the result shows that the system produces 2,5-di-n-butylamino-3,6-dichloro-p-benzoquinone via the chloranil anion and the n-butylamine cation with the rate constant of 9.8×102 sec−1mol−1l at 275.2°K. On the basis of reaction mechanisms, the reactions of various aliphatic amines with p-benzoquinone and its chloroderivatives were classified into five types. Stabilization energies due to the amino-substitution of p-benzoquinone were calculated by the composite molecule method; the result shows that the 2,5-derivative is most stable among the disubstituted p-benzoquinones.
  • Yoshiro Yonezawa, Takayuki Fueno
    1971 Volume 44 Issue 11 Pages 2976-2980
    Published: 1971
    Released: March 27, 2006
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    The multi-state semiclassical method proposed by Sharp and Rapp for calculating the vibrational transition probabilities of harmonic oscillators in collision was extended to Morse oscillators. Model calculations have been carried out for the excitation of a vibrational ground-state hydrogen molecule colliding with a helium atom at varying relative velocity. It has been shown that the Morse oscillator model gives greater transition probabilities than the corresponding harmonic oscillator model.
  • Tooru Taga, Norio Masaki, Kenji Osaki, Tokunosuke Watanabé
    1971 Volume 44 Issue 11 Pages 2981-2984
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of bis(o-ethoxyphenyl)butadiyne has been determined by the statistical method of X-ray analysis. The space group is P21a with two molecules in the unit cell of dimensions a=14.64, b=11.27, c=5.19 Å, and β=105.6°. The crystal structure is built up from columns of the molecules packed along the c-axis. The molecule has a center of symmetry and is almost planar. The diacetylene group is slightly twisted and the three conjugated bond distances of the diacetylene group are 1.434, 1.201, and 1.371 Å.
  • Yoshikazu Torihashi, Yoshifumi Furutani, Kiyoshi Yagii, Noboru Mataga, ...
    1971 Volume 44 Issue 11 Pages 2985-2989
    Published: 1971
    Released: March 27, 2006
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    The effects of high pressure on the charge-transfer (CT) absorption and fluorescence spectra of tetracyanobenzene (TCNB) complexes at room temperature have been examined. The pressure-induced change in the absorption intensity indicated the reduction of the distance between donor and acceptor in the complex and the increase in the overlap between their electron clouds. The pressure-induced red shifts of the absorption and fluorescence spectra were almost equal to each other in the case of the TCNB-toluene system, but the former shift was larger than the latter shift in the case of the TCNB-mesitylene system. These results were interpreted in terms of the reduction of the donor-acceptor distance in the complex as well as in terms of electrical solute-solvent interactions. It has been confirmed that the fluorescence quantum yield and the decay time of the complex decrease with the increase in the pressure, and that the rate of the decrease of the former is much larger than that of the latter, in the case of TCNB-toluene system. These results have been interpreted as being due to the pressure-induced increase in the quenching process at the Franck-Condon excited state as well as in the course of the relaxation process from the excited Franck-Condon state to the equilibrium fluorescent state.
  • Yuzo Sakurai, Takaharu Onishi, Kenzi Tamaru
    1971 Volume 44 Issue 11 Pages 2990-2993
    Published: 1971
    Released: March 27, 2006
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    The mercury photosensitized reaction of propylene-cis-1-d1 and 1-butene-cis-1-d1 was studied by means of microwave spectroscopy combined with gas chromatography and mass spectrometry. At pressures above 100 mmHg cis-trans isomerization was the main reaction for both the propylene and 1-butene. The number of the absorbed quanta of photons and the number of molecules reacted was almost equal. However, at lower pressures, this condition was not satisfied. At pressures less than 30 mmHg, substantial amounts of the 2-d1 and 3-d1 propylene species were detected in the reaction mixtures. Decomposition of propylene into an allylic radical and a hydrogen atom with subsequent “recombination,” was proposed to account for this observation. Similar results were obtained with 1-butene-cis-1-d1.
  • Hiroyuki Ishitobi, Hiroshi Tanida, Kazuo Tori, Teruji Tsuji
    1971 Volume 44 Issue 11 Pages 2993-3000
    Published: 1971
    Released: March 27, 2006
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    Cycloaddition of cycloheptatriene to maleic anhydride was re-examined and found to produce, in addition to the reported main product anti-tricyclo[3.2.2.02,4]non-6-endo-8,endo-9-dicarboxylic anhydride (1), the exo, exo isomer of this compound (4) and bicyclo[3.2.2]nona-2,6-diene-endo-8,endo-9-dicarboxylic anhydride (5). Evidence for these structures involving the orientation of the cyclopropane ring in 1 and 4 and the configuration of the carboxylic anhydride was provided by PMR spectroscopy using the intramolecular nuclear Overhauser effect and paramagnetic induced shift due to tris(dipivalomethanato)europium(III). The structure assignment by Alder and Jacobs for 1 was found to be correct, but not the one by Schenk et al The difference in free energies of activation leading to 1 and 4 was determined.
  • G. Chandra, S. N. Srivastava
    1971 Volume 44 Issue 11 Pages 3000-3003
    Published: 1971
    Released: March 27, 2006
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    The kinetics of Ag(I) ion catalysed oxidation of glycine by peroxodisulphate in aqueous medium has been studied. The reaction is found to be first order in peroxodisulphate and Ag(I) ions and almost independent of glycine concentration. The rate constant is found to decrease with the increase in the concentration of peroxodisulphate ion. Addition of neutral salts shows a retarding effect. A suitable mechanism has been proposed and a theoretical rate law has been derived to account for the results.
  • Ken Kashiwadate, Yasuo Saito, Akira Miyamoto, Yoshisada Ogino
    1971 Volume 44 Issue 11 Pages 3004-3009
    Published: 1971
    Released: March 27, 2006
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    In order to investigate the catalytic activity of molten metals, the dehydrogenation reactions of n-butyl alcohol, iso-butyl alcohol, and sec-butyl alcohol were carried out in the presence of molten zinc and molten indium (molten gallium was also used for the dehydrogenation of iso-butyl alcohol). According to the experimental results, all of these molten metals showed persistent catalytic activities and high selectivities for all the test reactions, and the decreasing order of the reactivity of the butyl alcohol isomers was found to be sec-butyl alcohol > iso-butyl alcohol > n-butyl alcohol. Among the three molten metals, i.e. Zn, Ga, and In, the activity and the selectivity of the molten zinc catalyst was outstandingly high. Further, kinetic analyses of the data showed that a compensation effect exists between the apparent activaiton energy, Ea, and the logarithmic frequency factor, logA.
  • Kiyoshi Niwa, Hiroaki Takahashi, Keniti Higasi, Teruo Kajiura
    1971 Volume 44 Issue 11 Pages 3010-3013
    Published: 1971
    Released: March 27, 2006
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    Infrared spectra of HgNH2Cl and HgNH2Br and the Raman spectrum of HgNH2Cl have been measured in the region from 4000 cm−1 to 30 cm−1. Effects of changing the X(X=Cl,Br) ion were observed mainly in N–H stretching bands and in lattice vibrations. Calculations of normal frequencies were carried out using a force field which includes inter-molecular forces. An assignment of the lattice vibrations was proposed and the force constants were also calculated. The force constants of the inter-molecular hydrogen bonds N–H···Cl and N–H···Br were obtained as 0.212 mdyn/Å and 0.142 mdyn/Å, respectively.
  • Ichiro Nakagawa
    1971 Volume 44 Issue 11 Pages 3014-3020
    Published: 1971
    Released: March 27, 2006
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    The reflection spectra of the crystals of the NaCl structure (LiF, NaF, and NiO), the fluorite structure (CaF2, BaF2, and CdF2), and the rutile structure (MgF2 and MnF2) were measured. The optical and dielectric constants were derived from the measured reflectivities using the Kramers-Kronig transformation. The absorption indices (k) for these crystals are rather large and the peak values of the imaginary dielectric constants amount to 30.0 or more. However, unlike the ferroelectric substances such as oxide perovskites and rutile, these fluoride crystals do not show any anomalous dielectric behaviour. From the real and imaginary dielectric constants ε′(ν) and ε″(ν), the transverse and longitudinal frequencies for the lattice modes are determined. These frequencies are reasonably interpreted on the basis of the crystal structures and satisfy the Lyddane-Sachs-Teller relation. The effective charge on the positive and negative ions and the force constant associated with the short-range elastic force against the ion displacement are obtained for the cubic crystals.
  • Hirotaka Shimanouchi, Yoshio Sasada, Tatsumichi Takeda
    1971 Volume 44 Issue 11 Pages 3020-3027
    Published: 1971
    Released: March 27, 2006
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    The structure of an Aconitum alkaloid, miyaconitine, C23H29O6N, has been determined by the X-ray analysis of crystals of the hydrobromide dihydrate, which are monoclinic with four formula units in a unit cell of the dimensions; a=10.41, b=13.85, c=9.63 Å and β=113.8°; space group, P21 The structure was solved by the heavy-atom method and was refined by the least-squares method. The final R index was 0.151. The absolute configuration was determined using the anomalous dispersion effect of the bromine atom. It was thus established that miyaconitine is a novel type of Aconitum alkaloid.
  • Osamu Tochiyama, Mutsuo Koyama, Taitiro Fujinaga
    1971 Volume 44 Issue 11 Pages 3028-3032
    Published: 1971
    Released: March 27, 2006
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    In connection with the liquid-liquid extraction study of alkali metal nitrophenolates, ionic equilibria taking place in the systems were studied by means of conductivity and solubility measurements. It was revealed that the adduct formation of p- and m-nitrophenolates consisted of homoconjugation, that is, free nitrophenols are attached not to cations, but to the nitrophenolate anions, thus forming the larger anions and being stabilized in the organic phase. Homoconjugation constants of the nitrophenolates, which are independent of the cations present, were measured. The difference in extraction behaviors was interpreted in terms of the solubilities in both aqueous and organic phases and in terms of the homoconjugation constants.
  • Reisuke Soda
    1971 Volume 44 Issue 11 Pages 3032-3035
    Published: 1971
    Released: March 27, 2006
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    By the gas-chromatographic analysis of the organic vapor in the air by means of a Porapak column, a broad peak accompanied by long tailing was observed at column temperatures above a certain value with a flameionization or an electron-capture detector. The cause of that peak was investigated using various gases and columns by changing the column temperature. The conclusion was that oxygen in air reacted with polymer beads even at temperatures lower than that cited in the catalogue as temerature to be employed, and the reaction products gave the anomalous broad peaks. The reaction was considered to consist of the oxygenation of polymer beads to produce carbon monoxide, carbon dioxide, formic acid, and the other organic compounds. For Porapak Q and P, the maximum temperature which can be used in safety may be 120°C for an analysis of a sample which consists in greater part of air.
  • Takeshi Tominaga, Takuhiko Sakai, Kitao Fujiwara
    1971 Volume 44 Issue 11 Pages 3036-3039
    Published: 1971
    Released: March 27, 2006
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    Thermal neutron irradiation has been carried out on the solutions of tris(acetylacetonato) cobalt(III) in benzene, ethanol, acetone and acetic acid containing various additives such as metallic salts and mineral acids. The 60Co retention in the irradiated solutions has been found to decrease sharply with the increase in the concentration of various metallic salts. This indicates that the thermal diffusive reactions which contribute greatly to the apparent retention in the irradiated solutions can be suppressed by the addition of adequate metallic salts as scavengers. Salts of the metals which can form more stable complexes with acetylacetone (i.e., Fe(III), Cu(II), Al(III), etc.) work as more effective scavengers in these systems. The upper limit for the primary retention of tris(acetylacetonato)cobalt(III) in the benzene solutions has been estimated as 0.00±0.02%. The use of adequate scavengers appears to be a useful technique to determine the primary retention in the irradiated solution systems. The 60Co retention of the solid complex irradiated at dry ice temperature was 1.4–1.5% irrespective of the organic solvents used for dissolution if they contain ferric chloride, while it increased to 2.0% in the absence of the scavenger.
  • Takeshi Katayama, Haruo Miyata, Kyoji Tôei
    1971 Volume 44 Issue 11 Pages 3040-3043
    Published: 1971
    Released: March 27, 2006
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    In order to clarify the effect of the hydroxyl group at the 5-position of chromotropic acid on the chelate stabilization, the following six reagents were synthesized by the coupling with 4-hydroxynaphthalene-2,7-disulfonic acid or 4,5-dihydroxynaphthalene-2,7-disulfonic acid(chromotropic acid): 2-(m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(I), 2-(o-methoxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(II), 2-(o-hydroxy-m-sulfophenylazo)-1-hydroxynaphthalene-3,6-disulfonic acid(III), 2-(m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(IV), 2-(o-methoxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(V), and 2-(o-hydroxy-m-sulfophenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid(VI). The acid dissociation constants of these reagents and the stability constants of their metal chelates with magnesium and calcium were measured by the pH titration method at an ionic strength of 0.10 and at 25°C. From the results obtained, it has become apparent that the hydroxyl group at the 5-position exerts a remarkable influence on the chelation of metal ions with the bidentate ligand, such as 2-(m-sulfophenylazo)-chromotropic acid, but that it has very little effect on those ions with the terdentate ligand, such as 2-(o-hydroxy-m-sulfophenylazo)-chromotropic acid. Such an effect appears even in the bidentate ligand with the methoxy group at the ortho-position of the benzene ring. That is to say, it may be concluded that the effect of the number of the chelate ring formed with a metal ion is preferred to stabilize the metal chelate over the effect of the hydroxyl group at the 5-position in the terdentate ligand.
  • Masataka Wakihara, Takashi Katsura
    1971 Volume 44 Issue 11 Pages 3043-3046
    Published: 1971
    Released: March 27, 2006
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    The phase equilibria in the FeO–Fe2O3–V2O3 system have been determined at 1500°K by varying the oxygen partial pressure. The following three oxide phases have been stable in equilibrium: a sesquioxide solid solution with a corundum-type structure (approximate composition Fe2O3–V2O3), a ternary solid solution with a spinel type structure (approximate composition FeO·Fe2O3–FeO·V2O3), and a ternary wüstite solid solution with a periclase-type structure which dissolves vanadium ions up to about 10 mol per cent. The extent of the solid solution areas and the location of the oxygen isobars have been determined. The spinel phase coexisted partly with metallic iron and partly with the wüstite solid solution, corresponding to lower and higher iron contents respectively. The standard free energies of the Fe+V2O3+\frac12O2=FeV2O4 and 0.05 Fe+V2O3+Fe0.95O=FeV2O4 reactions to produce FeV2O4 have been calculated to be −45500±200 cal and −5800±400 cal respectively at 1500°K on the basis of the equilibrium oxygen partial pressure.
  • Akira Ohyoshi, Akinori Jyo, Tetsuo Shinohara
    1971 Volume 44 Issue 11 Pages 3047-3051
    Published: 1971
    Released: March 27, 2006
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    Kinetic studies of the americium(III) oxidation have been made in aqueous solutions. The reaction rates are dependent on the concentrations of hydrogen, peroxydisulfate and the silver ion as catalyzers, and on the reaction temperature. The period of induction observed in the initial stage of reaction varies with the concentration of the reactant and with the reaction temperature. The data follow this rate expression:
    −\fracd[Am(III)]dt=Kh(k1+k2[Ag+])[S2O82−][Am(III)]·1⁄[H+]
    where Kh is the dissociation constant of hydrogen peroxydisulfate, and where k1 and k2 refer to the silver-ion uncatalyzed and catalyzed paths respectively. The energies of activation were determined to be 28.6 kcal/mol for k1 and 17.4 kcal/mol for k2.
  • Fujio Mizukami, Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1971 Volume 44 Issue 11 Pages 3051-3055
    Published: 1971
    Released: March 27, 2006
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    New cobalt(III) complexes with 2,4-pentanediaminetetraacetate (2,4-ptnta4−) have been prepared. The optically active 2,4-ptnta4− (RR or SS) forms a sexadentate complex and determines the absolute configuration around the metal ion. The meso-2,4-ptnta4− (RS) coordinates to the metal ion as a quinquedentate with a free acetate branch. Such stereospecific formations of sexa- and quinquedentate complexes from the optically active and the meso 2,4-ptnta4− have been attributed to the steric regulation coming from the methyl groups on the α-carbon atoms.
  • Goro Wada, Michiko Aoki
    1971 Volume 44 Issue 11 Pages 3056-3060
    Published: 1971
    Released: March 27, 2006
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    The rate constants, kapp, of the electron transfer reaction between iron(II) and iron(III) in mixed solvents of DMSO and water were measured at various acid and DMSO concentrations at μ=0.50M and 25°C. The kapp decreased linearly with the increase in [DMSO] at a constant [H+] and increased linearly with the increase in 1/[H+] at a constant [DMSO]. The reaction is considered to proceed through two paths: Fe2++*Fe3+→Fe3+*Fe2+ and Fe2++*FeOH2+→FeOH2++*Fe2+, with the rate constants of kO and kH respectively. Both kO and kH were suppressed by the addition of DMSO to water because of the occurrence of molecular association between DMSO and water. The hydration number of DMSO in a very dilute aqueous solution was approximately six, as revealed by the cryoscopic measurements. The suppression of kO and kH was proportional to [DMSO], with a common proportional constant. Consequently, DMSO was deduced to destroy the chains of water molecules connected by hydrogen bondings and to interfere with the ease of hydrogen atom transfer between the reducing and oxidizing iron species. DMSO itself did not serve as a ligand to catalyze the reaction as N-methylacetamide, N,N-dimethylacetamide, and various other anions do.
  • Kazutoshi Yamada, Takeo Konakahara, Hirotada Iida
    1971 Volume 44 Issue 11 Pages 3060-3062
    Published: 1971
    Released: March 27, 2006
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    By the electron impact reaction of substituted 4-nitrodiphenyl ethers (1), the substituents on ring B of (1) cause a reasonable change in the intensity of fragment ions which result from the nitro→ nitrite ester rearrangement. There is a linear correlation of the M+–NO fragment ion intensity of (1) with the ionization potential of the molecules, and with Hammett σ constants. These evidences suggest that the charge of ring B will be free to migrate to ring A in the ion state, even if they are separated by O-atom.
  • Masuhiko Tamura, Jay K. Kochi
    1971 Volume 44 Issue 11 Pages 3063-3073
    Published: 1971
    Released: March 27, 2006
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    The reactions of transition metal halides (Mn, Fe, Co, Ni, Pd, Cu, and Ag) with the low-molecular-weight alkyl Grignard reagents in tetrahydrofuran and diethyl ether, especially in the presence of styrene were reinvestigated. An alkyl transition metal species formed in situ by metathesis decomposed to a dialkyl (oxidative dimerization) or to an alkene and an alkane (oxidative disproportionation). Silver(I) and copper(II) were particularly effective in oxidative dimerization of primary alkyl groups. Alkyl groups which contain no β-hydrogen were also coupled by iron, cobalt, nickel, palladium, and copper(I) halides with varying degrees of efficiency. Oxidative disproportionation was generally the more common route to decomposition for alkyl groups which have β-hydrogens. It seemed to proceed directly via a bimolecular interaction of alkylmetals or indirectly by elimination of a hydrido-metal species. If the latter added to an alkene reversibly, exchange was observed between Grignard reagent and alkene. Styrene was reduced to ethylbenzene during the reaction both in tetrahydrofuran and in diethyl ether in varying yield with transition metal halide and Grignard reagent. In addition to alkyl exchange, dehydrogenation of the ethereal solvent by active (reduced) metal species complicated the stoichiometry of decomposition as measured by the value of the empirical parameter, Q,(R). The selection of transition metal in addition to the temperature, solvent and triphenylphosphine was effective variables in promoting the efficiency of the exchange process.
  • Tomihiro Nishiyama, Fukiko Yamada
    1971 Volume 44 Issue 11 Pages 3073-3077
    Published: 1971
    Released: March 27, 2006
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    New six 2-oxo-3-aryl-5-methyl-1,2,3-oxathiazolidines and six 2-oxo-3-aryl-5-chloromethyl-1,2,3-oxathiazolidines have been prepared in good yields by the reactions of N-sulfinylanilines with propylene oxide and epichlorohydrin respectively in the presence of catalysts. The compounds obtained exist in isomeric cis and trans forms at the S=O bond. The configurations of their stereoisomers were discussed by means of NMR.
  • Teruaki Mukaiyama, Kazuhiko Saigo
    1971 Volume 44 Issue 11 Pages 3077-3080
    Published: 1971
    Released: March 27, 2006
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    It was found that three different types of products, phenylthiomethylpyridinium bromide, ethoxy-bis(phenylthio)-methane and ethyl ethoxy-bis(phenylthio)acetate were obtained by the reactions of pyridinium bromides, such as phenacylpyridinium bromide, acetonylpyridinium bromide and ethoxycarbonylmethylpyridinium bromide, with sulfenamides in ethanol, depending on the nature of the carbonyl carbon of the starting pyridinium bromides.
  • Mamoru Ai, Sadao Suzuki
    1971 Volume 44 Issue 11 Pages 3081-3085
    Published: 1971
    Released: March 27, 2006
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    In the present work, the vapor-phase partial oxidation of cis-2-butene, butadiene, furan, and maleic anhydride was carried out over MoO3–P2O5 (1 : 0.2 atomic ratio) and MoO3–Bi2O3–P2O5 (1 : 1 : 0.2) with a contact time of 1.6 sec, at a concentration of 0.6–1.0%, and in air, in order to elucidate the difference between the two catalysts in their catalytic specificity for the oxidation of these reactants to maleic anhydride. Over the MoO3–P2O5 catalyst, the selectivities of butene, butadiene, and furan to maleic anhydride were 13, 50, and 78% respectively. Over the MoO3–Bi2O3–P2O5 catalyst, the formation of maleic anhydride from the reactants was very small, that of CO2 was important, and the rate of maleic anhydride destruction was fairly high. It is considered that the MoO3–Bi2O3–P2O5 catalyst has almost the same catalytic specificity as the MoO3–P2O5 in the C4H8→C4H2O3 step, but that its activity for maleic anhydride destruction is so high that maleic anhydride cannot be accumulated.
  • Seiji Shinkai, Toyoki Kunitake
    1971 Volume 44 Issue 11 Pages 3086-3090
    Published: 1971
    Released: March 27, 2006
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    Spontaneous hydrolyses of cationic and anionic phenyl esters in the presence of cholic acid (VI) and their catalytic hydrolyses with a histamine amide of cholic acid (VII) were investigated using a pH-stat at 30°C in 1.0M aqueous KCl. The rates of spontaneous hydrolysis decreased by 30–70% upon binding of substrates with cholic acid. The variation of the apparent binding constant (7-3650M−1) was considered to reflect the magnitude of hydrophobic forces between cholic acid and substrates, although the values may have to be corrected for the possible involvement of self-association of cholic acid molecules. Imidazole derivative VII catalyzed the hydrolysis of phenyl esters according to Michaelis-Menten kinetics. The long methylene chain in the substrate molecule contributed appreciably to the binding of substrate with cholic acid and its derivative. The magnitude of substrate binding with VII appears to be comparable to the true binding constant with cholic acid. The intracomplex rate constants did not differ much from those expected with other enzyme-like catalysts. Thus, the steroid ring seems to provide a non-specific hydrophobic binding site for the substrates used.
  • Jun-ichi Hayami, Nobuo Tanaka, Syuji Kurabayashi, Yasuhiro Kotani, Ari ...
    1971 Volume 44 Issue 11 Pages 3091-3095
    Published: 1971
    Released: March 27, 2006
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    The SN2 reactions having a symmetrical transition state were studied in a dipolar aprotic solvent. A good Hammett correlation was found for the chlorine isotopic exchange reactions in acetonitrile between tetraethylammonium chloride and three types of substituted methyl chlorides, 2-arylethyl chlorides, chloromethyl aryl ethers, and chloromethyl aryl sulfides. The reaction constant was positive for 2-arylethyl chlorides and negative for the methyl chlorides possessing an α-heteroatom. The presence of oxygen and sulfur atom on the α-position to the reaction center resulted in a rate enhancement of about 105 times and 103 times, respectively. Features of the transition states of these SN2 reactions are discussed.
  • Kenichi Hinoue, Masatomo Nojima, Niichiro Tokura
    1971 Volume 44 Issue 11 Pages 3096-3098
    Published: 1971
    Released: March 27, 2006
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    The rearrangement of 2-benzylidenecyclohexanone oxide (I) to 2-phenylcycloheptane-1,3-dione (II) was carried out in the presence of a Lewis acid or a Brφnsted acid in various media-liquid sulfur dioxide, benzene, and ether. The only reaction product of I with a Brφnsted acid in these solvents was the rearranged compound, II. In addition to II, 2-(α-halobenzyl)-2-hydroxycyclohexanone, (III) or (IV), was also obtained in the reaction of I with a Lewis acid in solutions. Drastic solvent effects were observed on the rate and the distribution of products in this reaction; however, no solvent effect was observed when a Brφnsted acid, which could donate a proton to I, was used as the catalyst. From the variations in the concentrations of the reactant, the intermediate, and the product during the reaction course, the solvent effects upon the reaction pathways were discussed.
  • Kyoji Kaeriyama, Yukio Yamazaki
    1971 Volume 44 Issue 11 Pages 3099-3101
    Published: 1971
    Released: March 27, 2006
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    The addition of 1,10-phenanthroline accelerates the polymerization of methyl methacrylate by a β-diketonato chelate of Cu(II), Mn(II), Mn(III), Co(II), Co(III), and Fe(III), but has no effect on the chelate of Ni(II). The effect of 1,10-phenanthroline, which is composed of two pyridine units, is much greater than that of pyridine. The polymerization rate of methyl methacrylate by the bis(benzoylacetonato)Cu(II)-1,10-phenanthroline system may be represented as follows:
    Rp∝ [MMA]{[Cu(II)][1,10-phenanthroline]}1⁄2
    The initiation reaction is assumed to be by a ligand-exchange reaction of bis(benzoylacetonato)Cu(II) with 1,10-phenanthroline, where a benzoylacetonyl ligand is displaced by 1,10-phenanthroline and Cu(II) is simultaneously reduced to Cu(I).
  • Hiroo Inoue, Tadao Ochiai, Akira Sugimoto, Eiji Imoto
    1971 Volume 44 Issue 11 Pages 3101-3106
    Published: 1971
    Released: March 27, 2006
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    The Photo-irradiation of a solution of 1- or 2-benzoyloxyphenazine in 2-propanol, followed by aeration, affords 1- or 2-hydroxyphenazine, benzaldehyde, isopropyl benzoate, and/or benzoic acid as the reaction products. The spectral change of the solution in the reaction process gives evidence of the fission of the acyl-to-oxygen bond. The addition of ferric chloride or dimethyl sulfate to the reaction system containing 1-benzoyloxyphena-zine in 2-propanol leads to the formation of isopropyl benzoate. When methanol instead of 2-propanol is used as the solvent, methyl benzoate is produced mainly. In cyclohexene as a hydrogen-donating solvent, benzaldehyde and an oxetane are obtained. The irradiation of a solution of 1-benzoyloxyphenazine in t-butyl alcohol or benzene gives no product, and the starting material is recovered in a 90–100% yield. 1-Benzoyloxyphenazhydrin, a photo-reduction intermediate, does not contribute to the formation of benzaldehyde. The intermediary formation of a semiquinoid form during irradiation brings about the fission of the acyl-to-oxygen bond, thus affording the corresponding aldehyde.
  • Hiroshi Yoshida, Tsuyoshi Ogata, Saburo Inokawa
    1971 Volume 44 Issue 11 Pages 3106-3108
    Published: 1971
    Released: March 27, 2006
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    The reaction of O-methyl-, ethyl-, and benzylxanthates with a catalytic amount of triethylamine in the presence of excess carbon disulfide gave the corresponding trithiocarbonate in good yields. The products were formed by the nucleophilic reaction of SCSSR with xanthates. The kinetic study showed the following order of nucleophilicity toward xanthates in DMF:
    SCOSMe>SCSSMe>Me3N
  • Hirohiko Katsuki, Tsuya Yoshida, Jun Nagai, Shozo Tanaka
    1971 Volume 44 Issue 11 Pages 3108-3112
    Published: 1971
    Released: March 27, 2006
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    Visible and infrared spectra and some other properties of cis and trans isomers of 2,4-dinitrophenylhydrazones of some aliphatic α-keto acids have been studied. It was observed that absorption maximum of the cis isomer in visible region occurred at a longer wavelength than that of the trans isomer in ethyl acetate as well as in bicarbonate solution and vice versa in sodium hydroxide solution. In infrared region, N–H and C=O stretching bands of the cis isomer were found at longer wavelengths than the corresponding bands of the trans isomer. It was concluded that a hydrogen bond is formed between C=O and N–H groups in the cis isomer. Further evidence which supports the above conclusion was given by the difference between both isomers in the nickel complex forming reaction, sodium carbonate reaction and in the properties of sodium salt. Instability of the trans isomer appeared to increase as the number of carbon atoms in the keto acid molecule increased. 2,4-Dinitrophenylhydrazones of some other α-keto acids were found to give polymorphs but not geometrical isomers.
  • Yoichiro Nagai, Hideyuki Matsumoto, Masaki Hayashi, Eiji Tajima, Hamao ...
    1971 Volume 44 Issue 11 Pages 3113-3116
    Published: 1971
    Released: March 27, 2006
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    Relative rates of hydrogen abstraction from Si-H bonds of α-substituted hydrosilanes by the trichloromethyl or the dichloromethyl radical were determined by allowing the hydrosilanes to compete in pairs for a chlorocarbon compound, carbon tetrachloride or chloroform, at 80°C in the presence of benzoyl peroxide. Results show that relative rates of the investigated hydrosilanes toward the trichloromethyl and the dichloromethyl radicals are satisfactorily correlated with the summation of Taft σ values for the substituent on the central silicon atom, giving ρ values of −0.11 and −0.08, respectively. Linear correlations are also found to exist between the relative rates and the 29Si-H coupling constants.
  • Yoko Naya, Munio Kotake
    1971 Volume 44 Issue 11 Pages 3116-3120
    Published: 1971
    Released: March 27, 2006
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    Evidence is presented for the volatile constituents of hops, not only in the resin glands, the so-called lupulin, but also in the stalk with leaves and in the three crops of cones during ripening. Lupulin shows a specific accumulation of myrcene, and the amount of the volatile constituents increases from fifty times to eight hundred times that in any other part of the plant in the course of ripening. While ripe cones contain neither any germacratrienes, the precursors of several sesquiterpenes, nor any aliphatic aldehydes, the stalk with leaves and the young cones have quite high concentrations of them respectively. Observation suggests that some of the volatile constituents are formed a t an early stage of growth, whilst others are formed later.
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