Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 4
Showing 1-50 articles out of 80 articles from the selected issue
  • Teizo Kitagawa, Keiichi Ohno, Hiromu Sugeta, Tatsuo Miyazawa
    1972 Volume 45 Issue 4 Pages 969-975
    Published: 1972
    Released: March 27, 2006
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    Far infrared spectra (700∼40 cm−1) of ethyl methyl ether and deuterated species (CH3CH2OCD3, CD3CH2OCH3, CH3CD2OCH3, and CD3CD2OCH3) were measured in the crystalline, liquid and gaseous states and carbon tetrachloride solution. A low temperature cell was constructed for measuring far infrared absorption of highly volatile samples in the liquid and crystalline states. Far infrared bands due to skeletal bending vibrations of the trans and gauche isomers and lattice vibrations were assigned. From analyses of isotope effects on infrared frequencies, internal-rotation vibrations of the CH3-CH2, CH2-O, and O-CH3 bonds of the trans isomer of ethyl methyl ether were found at 248, 115, and 202 cm−1, respectively, in the gaseous state. Normal vibrations were treated with the local-symmetry force field and force constants were adjusted by the method of least squares. By the use of Mathieu equation, the threefold potential barriers of the methyl groups of the trans isomer were estimated as V3(CH3-C)=3.3±0.1 and V3(O-CH3)=2.5±0.1 kcal/mol.
  • Yasuo Ueno, Isamu Sano
    1972 Volume 45 Issue 4 Pages 975-980
    Published: 1972
    Released: March 27, 2006
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    The aerosols obtained by spraying an aqueous Na2SO4 solution of concentrations ranging from 0.1 to 10% by weight were dried by a furnace at 200 to 800°C and were then subjected to stirred aging at room temperature in an atmosphere of 90% relative humidity or less; the variations in both mass concentration and particle size were then measured with the lapse of time.
    By employing the results thus obtained and by making some assumptions, the density of the particle in dried aerosols was calculated to be several tenths of one gram per cc, which is smaller by a factor of 3 to 4.5 than the bulk density of solid Na2SO4; further, the amount of water which the dried particle might hold if kept in a humidified atmosphere was estimated, with the finding that the density of a particle would decrease with increase in its water content; for example, the density of the particle with composition of Na2SO4·10H2O would be 0.32 g/cc, smaller by a factor of 4 to 5 than the bulk density. In addition, the influence of water vapor on the stability of the dried aerosols was studied; it was found that the higher the humidity, the greater the rate of coagulation.
  • Yuzo Sakurai, Takaharu Onishi, Kenzi Tamaru
    1972 Volume 45 Issue 4 Pages 980-983
    Published: 1972
    Released: March 27, 2006
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    The exchange reaction between propylene and deuterium was studied over alumina. The rate of the reaction was expressed by Vex=k[PD2]0.5[PPro]0.0. In the initial stages of the reaction the cis- and trans-1 -d1 species of propylene were the only products of the exchange reaction, but the concentration of the 3-d1 species increased continuously as the reaction progressed. The activation energy for the exchange reaction was about 8.2 kcal/mol.
    Propylene-cis-d1 was reacted over alumina, and the variation in the deuterium distribution of the propylene was followed by microwave spectroscopy. Isotope scrambling and “double-bond migration” occurred to considerable extents, while cis-trans equilibration between the two C1 hydrogen positions proceeded even faster. In the reaction of propylene-3-d1 the isotope mixing and “double-bond migration” were considerably slower than those of the cis-1-d1 species. Cis- and trans-1-d1 species were formed in equal amounts. The possible mechanism of these reactions is discussed on the basis of the results obtained.
  • Takeshi Sawai, Yoshiharu Shinozaki, Gisuke Meshitsuka
    1972 Volume 45 Issue 4 Pages 984-987
    Published: 1972
    Released: March 27, 2006
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    The trapped electron yields in alcohols and methanol-water mixtures at 77°K as a function of the electron scavenger concentration have been measured. The reciprocal of the trapped electron yield increased linearly with the concentrations of phenol, acetone, and acrylamide. The relative trapping efficiency for electrons was found to increase with an increase in the dielectric constant of the matrix at room temperature. The relative travelling distance of electrons in these matrices was also estimated.
  • Takayoshi Kobayashi, Saburo Nagakura
    1972 Volume 45 Issue 4 Pages 987-992
    Published: 1972
    Released: March 27, 2006
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    The quantum-yield ratios of phosphorescence to fluorescence and the phosphorescence lifetimes were measured for the charge-transfer complexes of tetracyanobenzene with methyl-substituted benzenes. By combining the observed results with the fluorescence quantum yields and lifetimes reported previously, the upper and lower limits of the rate constants for the intersystem crossing and for the radiative and non-radiative energy-transfer processes from the lowest triplet state to the ground state were obtained with the complexes. The intersystemcrossing rate constant of tetracyanobenzene was found to be decreased by the complex formation. This tendency was explained by the mixing of the charge-transfer configuration with the appropriate singlet and triplet states of the component molecules. The phosphorescence radiative rate constant was found to be determined by the contribution of the higher excited singlet configurations of each complex to the phosphorescent state. The temperature dependence of the phosphorescence-quenching rate constant was determined, and the activation energy of the process was interpreted as being due to intramolecular out-of-plane bending vibrations.
  • Naohiko Mikami, Mitsuo Ito
    1972 Volume 45 Issue 4 Pages 992-996
    Published: 1972
    Released: March 27, 2006
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    Polarized absorption spectrum of the second S→T transition of phenazine single crystal was measured at 4.2°K. The transition moments of the individual vibronic bands were determined uniquely from their polarization characteristics. The 0—0 band at 20470 cm−1 was found to be polarized along the N-N axis of the molecule and assigned as 3B3u1Ag(n*) transition. The vibronic bands other than the 0?0 band was found to be exclusively polarized along the long axis of the molecule, and they were assigned as the vibronic bands induced by a nontotally symmetric vibration in the 3B3u state. The possible routes of vibronic spin orbit coupling mechanism are discussed on the basis of the observed results.
  • Koichi Ohno, Takashi Kajiwara, Hiroo Inokuchi
    1972 Volume 45 Issue 4 Pages 996-1004
    Published: 1972
    Released: March 27, 2006
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    The fluorescence and absorption spectra of coronene dissolved in organic solvents were measured at room temperature. Their vibrational structures were analyzed by reference to the Raman lines of crystalline coronene measured by means of a He-Ne gas laser, and the observed transition energies were compared with the calculated ones. It was suggested that the p-band of the absorption spectrum of coronene (23000–27000 cm−1) is composed of more than one electronic transition, in contrast with the case of benzene. The fluorescence and phosphorescence spectra of coronene in n-octane were also measured at 77°K, and their vibrational structures were successfully analyzed with some perturbing vibrations and a few totally-symmetric ones.
  • Yasumasa J. I’haya, Toru Yunoki, Noboru Suzuki
    1972 Volume 45 Issue 4 Pages 1004-1010
    Published: 1972
    Released: March 27, 2006
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    Polarized absorption spectra of TCNNQ and TCNNQ-anthracene, pyrene, phenanthrene (Group 1), 1,2-benzanthracene, chrysene and triphenylene (Group 2) molecular complexes were measured in the frequency range of 13.5–42 kK at room temperature and 80°K. The mole ratio of donor to acceptor was found to be 2 : 1 for Group 1 complexes and 1 : 1 for Group 2 complexes. Two broad bands observed in each spectrum of these complexes were assigned to be the first and the second charge-transfer (CT) bands. The CT bands were enhanced in intensity and displaced to the red at 80°K. The first CT bands were confirmed to be associated with the charge transfer from the highest occupied molecular orbital (HOMO) of donor to the lowest vacant molecular orbital (LVMO) of acceptor. The charge transfer mechanism for the second CT bands may be divided into two classes; for Group 1 complexes it is mainly due to the second LVMO of acceptor, while for Group 2 complexes, in addition to this, there is a possibility of the charge transfer from the second HOMO of donor to the LVMO of acceptor.
  • Masayuki Nakagaki, Yoh Sano
    1972 Volume 45 Issue 4 Pages 1011-1018
    Published: 1972
    Released: March 27, 2006
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    Angular light-scattering investigations were carried out in 0.01 M sodium chloride solutions at 25°C for various mixed solutions of bovine serum albumin (BSA) and chondroitin sulfate (Chs). The experimental values of molecular weight and of the molecular dimensions showed an entirely different tendency from the calculated values, and we may assume that there is no interaction between them. It has, therefore, been concluded that Chs interacts with BSA strongly and that a complex is formed between them. For the soluble complex thus formed, the number of the bound BSA molecules with one Chs molecule was expressed by a Langmuir-type equation as a function of the amount of excess BSA existing free in the solution. When the latter was sufficiently large, the number of bound BSA molecules per Chs molecule approached 20.6.
    A Zimm plot of the complex was drawn, and the molecular weight, the radius of gyration, and the second virial coefficient of the complex were determined. It has been concluded from these results that the complex molecule has a long-like shape; the length was about 30% longer, but the diameter was about 6 times thicker, than the Chs molecule at the maximum binding of BSA.
  • Hiroyasu Inoue, Toshihiko Hoshi, Junko Yoshino, Yoshie Tanizaki
    1972 Volume 45 Issue 4 Pages 1018-1021
    Published: 1972
    Released: March 27, 2006
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    The π–π* electronic absorption spectra of 1-amino-, 1,4-diamino-, and 1,4,5,8-tetraaminoanthraquinones were investigated by means of the polarized absorption spectra using stretched PVA sheets and theoretical calculations. Each of these compounds has four absorption bands in the near-ultraviolet region (210–340 nm) and one in the visible region. The bands of the aminoanthraquinones which appear in the visible region can be assigned to the intramolecular charge-transfer transitions associated with the charge migration from the ami no group to the carbonyl groups.
  • Takeshi Nakajima, Azumao Toyota, Sadao Fujii
    1972 Volume 45 Issue 4 Pages 1022-1029
    Published: 1972
    Released: March 27, 2006
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    A symmetry rule for predicting molecular shapes which is based on the second-order Jahn-Teller effect has been applied to the predictions of bond distortions in a number of nonalternant hydrocarbons in their ground and electronically excited states. In spite of the very crude approximation that only the lowest-lying excited state plays a dominant role in determining the energetically most favorable nuclear displacement, a fairly clear-cut criterion for molecular-symmetry reduction was obtained. The actual types of the most soft bond distortions, determined by examining the two-center components of transition densities, are in good agreement with the results of variable bond-length SCF MO calculations and available experimental results. The problem of symmetry reductions possible in large cyclic polyenes C4n+2H4n+2 is briefly discussed.
  • Masamoto Iwaizumi, Takashi Matsuzaki, Taro Isobe
    1972 Volume 45 Issue 4 Pages 1030-1034
    Published: 1972
    Released: March 27, 2006
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    The ESR spectra of the 9,10-dihydrophenanthrene radical anion change drastically with the temperature, and at temperatures around −30°C the spectra show a marked line-width alternation effect. These temperature-dependent ESR spectra and the line-width alternation effect have been interpreted in terms of the conformational interconversion of the 9,10-dihydrophenanthrene radical anion molecule. From an analysis of the spectra, the activation energy of the inversion has been estimated to be 6.3±0.6 kcal/mol. It has also been estimated, from the ratio of the axial and equatorial proton splittings, that the dihedral angle of the axial protons is about 11°. These data are compared with those of the 4,5,9,10-tetrahydropyrene radical anion. The ESR of the 4,5-dihydropyrene radical anion is also presented.
  • Teijiro Tamura
    1972 Volume 45 Issue 4 Pages 1034-1038
    Published: 1972
    Released: March 27, 2006
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    The rates of the reaction of rhenium with nitric oxide under a filament temperature of (1300–1800)°K and a nitric oxide pressure of (3×10−5–1×10−3)Torr have been measured by a static method. The rate of the reaction increases with an increase in the temperature, and the apparent activation energy is 24 kcal/mol. The rate of the reaction is proportional to the nitric oxide pressure and independent of the nitrogen pressure. The apparent compositions of the rhenium oxide produced in the reaction have been determined from the weight change in the rhenium filament and from the amount of nitric oxide consumed in the temperature range of (1300–2100)°K. The ReO3 and Re2O7 were formed at lower temperatures and at higher temperatures respectively. The Re2O7 was presumed to be formed by the oxidation of the ReO3 deposited on the vessel wall with atomic oxygen evolved in a high-temperature range.
  • Masao Sakurai, Tsuyoshi Komatsu, Tsurutaro Nakagawa
    1972 Volume 45 Issue 4 Pages 1038-1044
    Published: 1972
    Released: March 27, 2006
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    The shifts in the temperature of the maximum density of water produced by the addition of small amounts of oligomers of polyethylene glycol and polyethylenimine and other related compounds were determined by dilatometry. These effects were interpreted in terms of the change in the structure of water around the various solute molecules in connection with their chain length. It was found that, as the chain length increases, the extent of the modification of the water structure by the chain molecules decreases because of the hydrophobic contact between ethylene groups. The apparent specific expansibility of the solute in the neighbourhood of 4°C was also evaluated as a function of the concentration.
  • Akio Morita, Hiroaki Takahashi, Keniti Higasi
    1972 Volume 45 Issue 4 Pages 1045-1049
    Published: 1972
    Released: March 27, 2006
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    Experiments to confirm Kubo’s conclusion on the complex formation of 1,2-dichloroethane with benzene were carried out following his procedure. Dielectric measurements were carried out with inert solvents hexane and cyclohexane. The interactions between 1,2-dichloroethane and each of the compounds toluene and p-xylene were also studied with inert solvents hexane, cyclohexane, and carbon tetrachloride. The results are discussed in relation to complex formation.
  • Okihiro Tokunaga, Kumao Hamanoue, Jiro Okamoto, Akibumi Danno
    1972 Volume 45 Issue 4 Pages 1050-1054
    Published: 1972
    Released: March 27, 2006
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    The γ-radiolysis of a gaseous mixture of ethylene and ammonia has been investigated over the whole range of composition. The products of decomposition were primarily hydrogen, ethane, n-butane, ethylamine, and acetylene. It was observed that the yields of ethane, n-butane, and ethylamine increased with the increasing concentration of ammonia, and that the G-values of these products at 98 mol% ammonia were 0.52, 2.12, and 0.89, respectively. Addition of oxygen or nitric oxide as radical scavengers tended to reduce the yields remarkably. The G-value of ethyl radical was calculated from the G-values of ethane, n-butane, and ethylamine, and the limiting value of G(C2H5·) was determined by extrapolation to 100 mol% ammonia. The value thus obtained agrees with the initial G-value of hydrogen radical, i.e., GH=7.0±0.6, which was obtained by Eyre and Smithies in the study of the γ-radiolysis of ammonia gas. From these results, it was concluded that thermal hydrogen radicals produced by the γ-radiolysis react quickly with ethylene, giving ethane, n-butane, and ethylamine from ethyl radicals.
  • Toshiro Asakawa, Motomichi Inoue, Ken-ichi Hara, Masaji Kubo
    1972 Volume 45 Issue 4 Pages 1054-1057
    Published: 1972
    Released: March 27, 2006
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    The magnetic susceptibilities of bis(6-aminopurinato)copper(II) trihydrate, dichlorobis(6-aminopurine)copper (II) sesquihydrate, and dichlorobis(6-hydroxypurine)copper(II) monohydrate obey the Bleaney-Bowers equation for binuclear clusters in conformity with the results of X-ray crystal analysis. The exchange integrals within binuclear clusters were evaluated as Jk=−156 to −208°K. Superexchange interaction rather than the interaction of direct nature operates predominantly between copper atoms through the pπ orbitals of the heterocycles. The Jk values of the compounds are nearly equal to the value, −204°K, of copper(II) acetate monohydrate, although the Cu–Cu distance in the former is greater than that in the latter. The magnetic susceptibilities of dibromobis(6-aminopurine)copper(II) dihydrate, dibromobis(6-hydroxypurine)copper(II) dihydrate, dichloro(6-aminopurme)copper (II), dichloro(6-hy droxypurine)copper (II) monohydrate, and dibromo(6-hydroxypurine)copper(II) hemihydrate indicate the presence of paired copper atoms in the crystals.
  • Makoto Watanabe, Mineo Kato
    1972 Volume 45 Issue 4 Pages 1058-1060
    Published: 1972
    Released: March 27, 2006
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    Glassy substances of the NaPO3-Sb2O3 and NaPO3-Sb2O5 systems with P/Sb ratios in the range from 5.0 to 300 were prepared by heating NaPO3 and Sb2O3, or Sb2O5 at 1000°C, and by then quenching the melts of the mixtures. The condensed phosphates were separated by paper-chromatographic analysis and determined colorimetrically, and the average degree of polymerization of the phosphates was measured by the pH-titration method. From these results, it has been found that the degree of polymerization of the phosphates increased with the increase in the P/Sb ratio. When the glassy samples of both the systems were treated with water, antimony trioxide was deposited. The results show that, in the glassy samples of both the systems, the valency of antimony is three, assuming that the glasses have the P–O–P, P–O, P–O–Sb, and Sb–O linkages, a theoretical treatment of the degree of polymerization of condensed phosphates has been made and compared with the experimental data. It has been concluded that the glasses of both the systems with P/Sb ratios larger than 5.0 have P–O–P, P–O, and P–O–Sb linkages.
  • Joseph Bagkes, Isao Masuda, Koichiro Shinra
    1972 Volume 45 Issue 4 Pages 1061-1064
    Published: 1972
    Released: March 27, 2006
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    Three polymeric iron(II)-tetraoxime chelates of the formula CH3C(NOH)C(NOH)-R-C(NOH)C(NOH)-CH3, where R: C6H4-O-C6H4, C6H4-C6H4, and 2,6-pyridyl, are characterized and compared with monomeric α-dioxime analogues. Analytical data indicate that in the solid state these Fe-N4 type chelates do not coordinate an axial base. Axial substitution takes place only upon dissolution into pyridine or similar basic solvents. The resemblance between the substituted polymer chelates and the monomeric dimethylglyoxime compounds, as far as their electronic spectra are concerned, is discussed. While the solid state polymers are all paramagnetic with moments 2.0–2.5 B.M., ESR data show that in solution a conversion into a diamagnetic species takes place. A strong absorption band due to the O–N stretching vibration appears at about 1650 cm−1 upon complexing of the nitrogen atoms. The paramagnetism and the reflectance spectra of the solid state samples are related to their structure.
  • Ryokichi Tsuchiya, Masatatsu Suzuki, Eishin Kyuno
    1972 Volume 45 Issue 4 Pages 1065-1068
    Published: 1972
    Released: March 27, 2006
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    The cis, trans-to-trans, cis isomerization as well as dehydration of [CoCl2(NH3)2en]Br·H2O were investigated by using derivatographic, isothermal, and sealed tube methods. Isomerization in a solid phase proceeded regardless of whether its state was monohydrate or anhydride. Two distinct processes were found for isomerization, one being accompanied by the liberation of water of crystallization and the other taking place after complete liberation of water of crystallization. Both reactions were of the first order. The thermochemical functions were obtained to be ΔH=(12±2) kcal/mol, E\ eweq=(28±3) kcal/mol and ΔS\ eweq=(−10±4) e.u. for dehydration. The values E\ eweq=(28±3) kcal/mol and S\ eweq(−4±2) e.u. were estimated for isomerization in the first process, and E\ eweq=(28±3) kcal/mol and ΔS\ eweq=(−12±3) e.u. for that in the second process. As a possible reaction mechanism for isomerization, an “aquation-anation mechanism” was introduced for the first process and an “intramolecular mechanism” for the second.
  • Hiroaki Tagawa
    1972 Volume 45 Issue 4 Pages 1069-1072
    Published: 1972
    Released: March 27, 2006
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    Formation of U2C3 by the reaction of UC2 with MgO has been studied by means of chemical and X-ray analyses at temperatures 1450–1700°C in vacuo. The reaction was found to proceed generating CO and Mg vapor and to produce U2C3. The decarburization is represented by
    2UC2+MgO→U2C3+CO+Mg.
    UO2 and UC were formed as the intermediate compounds. The amount of UO2 was nearly equal to that formed by the reaction: UC2+4MgO=UO2+2CO+4Mg. The lattice parameter of U2C3 was 8.0890 Å. The lattice parameters of UC2 and UC varied with the reaction time. The main reaction sequence was suggested to be:
    1⁄4UC2+MgO=1⁄4UO2+1⁄2CO+Mg
    7⁄4UC2+1⁄4UO2=U2C3+1⁄2CO.
    The experimental results were in good agreement with those obtained by thermochemical calculation.
  • Goro Wada, Akiko Endo
    1972 Volume 45 Issue 4 Pages 1073-1078
    Published: 1972
    Released: March 27, 2006
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    The electron-transfer reaction between Fe(II) and Fe(III) species in mixed solvents of methanol and water was investigated by the use of Fe-59 as the radioactive tracer. The hydrolysis constant of Fe3+, KH, in the mixed solvent decreases gradually as the mole faction of methanol, xM, increases. At very high acidities, ionic association between Fe3+ and ClO4 ions occurs, thus forming an ion-pair in the mixed solvent. The apparent rate constant, kapp, of the electron-transfer reaction is a function with respect to xM; kapp does not vary much in the concentration range xM≤0.3, but it decreases as xM grows higher than 0.3. kapp is also dependent upon [H+] and in a linear relationship with [H+]−1. Thus, the two reaction paths, Fe2+-Fe3+ (k0) and Fe2+-FeOH2+ (kH), are deduced to be prevailing. Both rate constants, k0 and kH, decrease with an increase in xM. The constancy of kapp at 0≤xM≤0.3 is a result of compensation between the increasing KH value and the decreasing k0 and kH values. By taking into account the values of ΔHH\ eweq=7.6 kcal/mol and ΔSH\ eweq=−19.1 e.u. at xM=0.2, both of which do not differ greatly from those in pure water, the reaction is concluded to proceed through the hydrogen-atom-transfer mechanism in the mixed solvent, the inhibiting effect of methanol being due to the reduction of the hydrogen bondings between water molecules.
  • Sigeo Kida, Takayuki Oniki
    1972 Volume 45 Issue 4 Pages 1078-1080
    Published: 1972
    Released: March 27, 2006
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    The complexes of Ni(II), Cu(II), and Co(III) with N,N-Dialkylethylenediamine (alkyl=CH3, C2H5, and C3H7) have been prepared. It was revealed that these ligands coordinate to metal ions as bidentate ligands with amino and tertiary amine oxide groups. Two forms have been obtained for the 1 : 2 nickel(II) complexes, the hydrated green form with μeff=3.3 and the anhydrous red or reddish brown form with zero or very low magnetic moment. They are easily convertible into each other. Formation of square planar diamagnetic Ni(II) complexes with ionic-type ligand was interpreted in terms of the steric effect of the alkyl groups.
  • Masakatsu Uyemura, Shiro Maeda
    1972 Volume 45 Issue 4 Pages 1081-1086
    Published: 1972
    Released: March 27, 2006
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    The absolute infrared intensities of crystalline HGN and DCN were measured at the temperature of liquid N2. In comparison with the gaseous values, both stretching fundamentals (v1, v3) exhibited a striking increase in the integrated absorption, while the bending (v2) was almost unchanged. From the observed intensity change, the change in the dipole-moment derivatives with respect to the molecular internal coordinates was calculated to be ∂ΔM⁄∂rC=N=1.43 D/Å and ∂ΔM⁄∂rC−H=2.01 D/Å, those values were chosen from two alternative possibilities as the more probable set. The significance of these values, however, is somewhat peculiar to the optically-active crystalline vibrations, so they were then resolved into derivatives with respect to purely intramolecular and intermolecular coordinates: [∂ΔM⁄∂rC−H]=0.58 D/Å and [∂ΔM⁄∂rH···N]=−1.43 D/Å. The general intensity features were reasonably interpreted by considering the contribution of a charge-transfer structure to the H–N hydrogen bonding.
  • Masahiko Saburi, Tsutomu Sawai, Sadao Yoshikawa
    1972 Volume 45 Issue 4 Pages 1086-1093
    Published: 1972
    Released: March 27, 2006
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    Dinitrocobalt(III) complexes with (3S,8S)-dimethyltriethylenetetramine((3S,8S)-dimetrien) and related ligands were prepared and separated into the geometrical isomers. The cis-α and cis-β isomers of the (3S,8S)-dimetrien complex gave rise to the Λ and Δ isomers respectively. A similar stereospecificity could be observed for the other dissymmetric ligands employed in this study. The circular dichroism (CD) spectra of the cis-β isomers showed three kinds of patterns, which were related to the structural features of the complexes.
  • Masaaki Yamada, Shigetaka Suzuki, Shun Araki
    1972 Volume 45 Issue 4 Pages 1093-1097
    Published: 1972
    Released: March 27, 2006
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    Behavior of alkali metals in the small hydrogen flame for ultra-micro analysis of alkali and alkaline earth metals were investigated. Distribution of free neutral atoms and formation of alkali hydroxides were studied by the photometric method, distribution of charged particles was determined by the Langmuir probe method, and confirmation of whether negative-charged particles are mostly electrons or negative ions by the sheath method. It was found that only lithium formed hydroxide in the flame, ionization chiefly occurred in the part 0–5 mm above the jet, and that most of negative-charged particles are not electrons but negative ions.
  • Kenzo Nagase, Nobuyuki Tanaka
    1972 Volume 45 Issue 4 Pages 1097-1100
    Published: 1972
    Released: March 27, 2006
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    A simple method for the synthesis of trans-dichlorotetraamminechromium(III) chloride monohydrate was developed, and the configuration of the complex obtained was confirmed by measurements of the infrared and visible absorption spectra. It was found that the cis-trans isomerization took place in the solid state upon the thermal treatment of the complex at 200°C. The enthalpy change for the reaction was calculated to be 1.2 kcal·mol−1 by an analysis of the DSC curve.
  • Hiroshi Yokoi, Mitsuru Sai, Taro Isobe
    1972 Volume 45 Issue 4 Pages 1100-1104
    Published: 1972
    Released: March 27, 2006
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    Two types of thermochromisms have been found for several β-diketone chelate complexes of copper(II) in pure pyridine or γ-picoline. One is observed for such complexes as bis(acetylacetonato)copper(II). In this case, the visible absorption spectra at various temperatures have well-defined isosbestic points; there are two different complex species, L and H, at equilibrium in the solvent, where L and H represent the low-temperature and high-temperature species respectively; they are different in the interaction between the complex and pyridine or γ-picoline molecules. The other is observed for such complexes as bis(salicylaldehydato)copper(II), where the spectral intensity increases remarkably with a rise in the temperature. The equilibrium for bis(acetylacetonato)copper(II) was studied over the temperature range of 0–60°C, and the results were used to derive the approximate thermodynamic parameters, ΔH=4.0±1.0 kcal/mol and ΔS=13±4 e.u., for the L→H change. The most probable structures for L and H were suggested from a spectrophotometrical point of view.
  • Takakazu Yamamoto, Akio Yamamoto, Sakuji Ikeda
    1972 Volume 45 Issue 4 Pages 1104-1110
    Published: 1972
    Released: March 27, 2006
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    The reactions of dialkylbis(dipyridyl)iron (II) 1 with various substituted olefins were studied. Tetracyano-ethylene, maleic anhydride, and acrylamide gave olefin-coordinated π-complexes on reactions with 1, whereas other vinyl monomers with relatively large e-values were polymerized by the alkyl-iron complex. Kinetic study of the reactions of 1 with olefins by a spectroscopic method revealed that the reaction rate can be expressed by
    −\fracd[FeR2(dipy)2]dt=\frac[olefin][FeR2(dipy)2]A+B[olefin]+C[dipy]
    On the basis of kinetic results and from comparison with the reactions of dialkyl(dipyridyl)nickel with olefins, a mechanism involving partial dissociation of the dipyridyl ligand from 1, followed by a coordination of the olefin and activation of a Fe-alkyl bond was proposed.
  • Takakazu Yamamoto, Akio Yamamoto, Sakuji Ikeda
    1972 Volume 45 Issue 4 Pages 1111-1117
    Published: 1972
    Released: March 27, 2006
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    Kinetics of polymerization of vinyl compounds (acrylonitrile, methacrylonitrile, acrolein, methyl vinyl ketone, methyl acrylate, alkyl methacrylates, and 2-vinylpyridine) with dialkylbis(dipyridyl)iron(II), FeR2(dipy)2 1 (R=CH3, C2H5, n-C3H7), was studied. By comparison with previous kinetic results in which the decomposition of 1 was followed spectroscopically, a polymerization mechanism including a slow initiation process followed by rapid propagation and unimolecular termination processes was proposed. The effects of the concentration of monomer, the addition of dipyridyl and the coordinating ability of solvent on the molecular weight of the polymer were explained by competitive coordination to the iron complex having a growing polymer chain. Results of copoly-merization experiments were explained in terms of competitive coordination and insertion reactions between the monomers involved. A linear relationship was found between log(1⁄r1) values and the logarithms of stability constants of nickel-olefin π-complexes with methacrylonitrile as the reference (M1). From the formation of C2-H5D in the polymerization of β-cis-d1-methyl methacrylate with Fe(C2H5)2(dipy)2 a unimolecular termination process involving abstraction of β-hydrogens of the growing chain by the alkyl group or the iron complex was proposed.
  • Mamoru Nakai, Naomichi Furukawa, Shigeru Oae, Takeshige Nakabayashi
    1972 Volume 45 Issue 4 Pages 1117-1119
    Published: 1972
    Released: March 27, 2006
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    The photolysis of diphenyl sulfone-1-14C upon irradiation with 2537 Å light in benzene gave biphenyl-1-14C and benzenesulfinic acid-14C. The yields of both compounds were estimated by means of an isotope dilution method. The 14C activity of the sulfone recovered was equal to that of the sulfone employed, while that of biphenyl formed was found to have nearly one half of the 14C activity. These results reveal that the phenylation reaction by phenyl radical formed by the photolytic cleavage of the C–S bond of the sulfone is an intermolecular reaction in which benzenesulfonyl radical appears to abstract hydrogen from the intermediate cyclohexadienyl radical rather than attacking benzene. The 14C distribution indicates that the 14C activity at 1-position was found to remain at the same position of biphenyl after photolysis of the sulfone. Thus, the photolysis of diaryl sulfones in benzene followed by the oxidation of biphenyl derivatives obtained would be a convenient method for the degradation of diaryl sulfones.
  • Masuhiko Tamura, Jay K. Kochi
    1972 Volume 45 Issue 4 Pages 1120-1127
    Published: 1972
    Released: March 27, 2006
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    The reaction between various Grignard reagents and silver(I) salts in the presence of nitrogen-containing oxidants such as lithium nitrate, nitrogen dioxide, and methyl nitrate has been examined in tetrahydrofuran solutions. Coupling dimer is formed in high yields almost independently of the structure of the Grignard reagent. From the stoichiometry, it is concluded that these oxidants oxidize two equivalents of metallic silver formed in situ to silver(I) species under proper reaction conditions. Other transition metal halides are also oxidized by these oxidants in a similar manner. Soluble forms of reduced silver complexes formed in the reaction of silver(I) nitrate and Grignard reagent are also described.
  • Takenori Nishino, Masumi Kiyokawa, Yoshiyuki Miichi, Kanji Tokuyama
    1972 Volume 45 Issue 4 Pages 1127-1132
    Published: 1972
    Released: March 27, 2006
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    The reaction of 2-dimethoxymethyl-3-methoxypropionitrile (1) with acetamidine yields 2,7-dimethyl-5,6-dihydropyrimido[4,5-d]pyrimidine (6) via an intermediate, λmaxMeOH 262 mμ. This intermediate has been identified as 2-acetamidinomethylene-3-methoxypropionitrile (5) without being isolated. However, this assignment seems to be somewhat inconsistent with the stabilities of an acetal group in basic media and with the UV spectra of compounds with structures similar to 5. The reaction of 1 with sodium methoxide gave a dimeric compound (8). This result suggests the formation of 2-dimethoxymethylacrylonitrile (2) in the initial stage of the reaction of 1 with acetamidine. The reaction of acrylonitrlie with acetamidine yielded 2-methyl-4-amino-5,6-dihydropyrimidine (23), whose UV spectrum in methanol showed its absorption maximum at 270 mμ in neutral media and at 258 mμ in basic media. Therefore, the structure of the intermediate may be concluded to be 2-methyl-4-amino-5-dimethoxymethyl-5,6-dihydropyrimidine (27) instead of 5, and the reaction may be concluded to proceed via the pathway of 12276.
  • Kazu Kurosawa, Junko Higuchi
    1972 Volume 45 Issue 4 Pages 1132-1136
    Published: 1972
    Released: March 27, 2006
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    2′-Hydroxychalcones were oxidized with lead tetraacetate and manganic acetate to give trans- and cis-aurones, together with substituted benzoic acids and cinnamic acid. In the oxidation, 2′-benzyloxy-4,4′-dimethoxychal-cone gave 2-acetoxy-l-(2′-benzyloxy-4′-methoxy)phenyl-3-(4′-methoxy)phenylpropane-1,3-dione and erythro-2,3-diacetoxy-1-(2′-benzyloxy-4′-methoxy)phenyl-3-(4′-methoxy)phenylpropan-l-one. Structures of the products were elucidated spectrometrically and confirmed by syntheses.
  • Takeshi Matsumoto, Haruhisa Shirahama, Akitami Ichihara, Hyonsobb Shin ...
    1972 Volume 45 Issue 4 Pages 1136-1139
    Published: 1972
    Released: March 27, 2006
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    Several promising cyclopropane intermediates in the total synthesis of illudin M and S have been prepared. Survey of NMR of these compounds showed the conformation 17 to be unfavourable.
  • Takeshi Matsumoto, Haruhisa Shirahama, Akitami Ichihara, Hyonsobb Shin ...
    1972 Volume 45 Issue 4 Pages 1140-1144
    Published: 1972
    Released: March 27, 2006
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    5,5-Dimethyl-4-acetoxy-2-cyclopentenone and 5-methyl-t-5-acetoxymethyl-r-4-acetoxy-2-cyclopentenone, intermediates for illudin M and S respectively, have been synthesized from ethyl adipate.
  • Takeshi Matsumoto, Haruhisa Shirahama, Akitami Ichihara, Hyonsobb Shin ...
    1972 Volume 45 Issue 4 Pages 1144-1147
    Published: 1972
    Released: March 27, 2006
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    5,5-Dimethyl-4-acetoxy-2-cyclopentenone, an intermediate in the total synthesis of illudin M, has been prepared from 1-methylsulfinyl-3,3-dimethyl-4,4-ethylenedioxy-2-pentanone as well as from 1,1 -trimethylenedithio-3,3-dimethyl-4,4-ethylenedioxy-2-pentanone. An example of new intramolecular transketalization has been described.
  • Takashi Matsumoto, Gojo Sakata, Yakudo Tachibana, Kenji Fukui
    1972 Volume 45 Issue 4 Pages 1147-1152
    Published: 1972
    Released: March 27, 2006
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    The stereochemistry of the condensations of 2,2,6-trimethylcyclohexanone with t-butyl acetate in the presence of lithium amide, with ethyl bromoacetate in the presence of zinc (Reformatsky reaction), and with ethylmagnesium iodide (Grignard reaction) was studied. The configurations of the products in these reactions were assigned on the basis of their chromatographic behavior, and on the basis of spectroscopic and chemical studies of them. From the present experiments it is evident that all of these nucleophilic addition reactions proceed in a similar fashion. Further, the treatment of t-butyl 1-hydroxy-2,2,t-6-trimethyl-r-1-cyclohexaneacetate (IIa) with potassium hydrogensulfate or with dilute sulfuric acid gave (±)-cis-tetrahydroactinidiolide (IX), which was isolated from the essential oil of cigar tobacco leaves by Kaneko and Hoshino, while the treatment of IIa with isopropenyl acetate in the presence of p-toluenesulfonic acid gave a mixture of IX and its trans-isomer (X).
  • Hideo Hasegawa, Mamoru Imanari, Kazuhiko Ishizu
    1972 Volume 45 Issue 4 Pages 1153-1158
    Published: 1972
    Released: March 27, 2006
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    Carbon-13 NMR spectra were observed for the seventeen alkyl biphenyls. For the meta- and para-alkyl derivatives, the observed ring carbon-13 chemical shifts could be adequately understood in terms of the Karplus-Pople’s formula by taking into account the hyperconjugative effect of the substituents. The observed chemical shifts of aliphatic carbon were in good agreement with the values of the corresponding alkylated benzenes within the limits of experimental error. For the ortho-derivatives, the conformation of substituents in the hindered biphenyls was particularly discussed in relation to the observed alkyl carbon-13 chemical shifts. In the cases of 2,2′-dimethylbiphenyl and 2,2′,6,6′-tetramethylbiphenyl, the chemical shifts of methyl carbons at the ortho-position revealed a high field shift of about 1 ppm, but that of 2,4,6-trimethylbiphenyl indicated only 0.4 ppm. The different shifts of the ortho-methyl carbons in the two cases suggested a spece interaction between the two methyl groups. This interaction may arise an orbital overlap between the methyl groups, which were considered to approach one another to take the cis-conformation.
  • Yasuzo Uchida, Masanobu Hidai, Takashi Tatsumi
    1972 Volume 45 Issue 4 Pages 1158-1161
    Published: 1972
    Released: March 27, 2006
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    ReCl5 was activated with Et3Al and oxygen to give a catalyst effective for the disproportionation of α-olefins as well as internal olefins. The catalyst species was deactivated by excess oxygen. The catalyst system consisting of either WCl6 or MoCl5 and Et3Al exhibited disproportionation activity in a short range of Al/M (M=W or Mo) molar ratio. The activity decreased with the increase in the Al/M ratio, but was restored by the introduction of oxygen.
  • Yasuo Nakagawa, Takashi Tsuno, Kiichiro Nakajima, Michio Iwai, Haruki ...
    1972 Volume 45 Issue 4 Pages 1162-1167
    Published: 1972
    Released: March 27, 2006
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    The β-elimination reaction of the O-tosyl β-hiydroxy amino acid peptide derivative was thoroughly investigated. The N-tosyl-L-serylglycine ester and the N-tosyl-L-threonylglycine ester gave the N-tosyl-L-aziridinecarbonyl-glycine ester and the N-tosyl-3-methyl-L-aziridinecarbonylglycine ester as the resulting products respectively by the elimination reaction. On the other hand, the N-carbobenzoxyglycyl-L-serylglycine ester was not converted into the aziridine peptide derivative; only the dehydroalanine peptide was obtained. However, the N-tosyl-L-phenylalanyl-L-threonylglycine ester and the N-carbobenzoxyglycyl-L-threonylglycine ester were converted into the corresponding aziridine peptide, and the N-tosyl-L-phenylalanyl-3-methyl-L-aziridinecarbonylglycine ester and the N-carbobenzoxyglycyl-3-methyl-L-aziridinecarbonylglycine ester were obtained respectively. It was concluded that the peptides containing threonine were easily converted into the aziridine peptides and not the serine peptides by the β-elimination reaction.
  • Yasusi Yamamoto, Hitosi Nozaki
    1972 Volume 45 Issue 4 Pages 1167-1169
    Published: 1972
    Released: March 27, 2006
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    Bis-β-keto sulfoxides of the MeSOCH2CO(CH2)nCOCH2SOMe (n=7, 8, or 10) type are prepared. The dl and meso isomers are isolated, and the stereochemistry of bis-β-keto sulfoxides (n=8) is established by means of the asymmetric synthesis of the resolvable isomer from an optically-active ester, (−)-menthyl–O–CO(CH2)8–CO–O–(−)-menthyl, and methylsulfinylcarbanion. It is concluded that the higher-melting one is the meso isomer and that the lower-melting one is racemic. The condensation of bis-β-keto sulfoxides, MeSOCH2CO(CH2)8-COCH2SOMe, and allyl bromide in the presence of a base and the subsequent desulfurization give the olefinic ketone, (CH2=CHCH2CH2CO(CH2)4)2. Optically active sulfoxide, MeSOCH2COPh, is obtained from (−)-menthyl benzoate and methylsulfinylcarbanion.
  • Chyongjin Pac, Takafumi Tosa, Hiroshi Sakurai
    1972 Volume 45 Issue 4 Pages 1169-1175
    Published: 1972
    Released: March 27, 2006
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    Irradiation of methanolic solutions of DMA containing halobenzenes (chlorobenzene, bromobenzene and iodobenzene) and triethylamine (TEA) gave TEA hydrohalides in quantitative yields along with benzene (II), di-phenyl, N-methylaniline, o- and p-dimethylaminodiphenyls (IV and V). From the properties of the products and spectroscopic and kinetic data, it was suggested that the reactions took place by way of electron transfer from DMA to halobenzenes. The electron transfer reactions were classified into a short range type (chlorobenzene and bromobenzene) and a long range type (iodobenzene) on the basis of the product ratio (IV+V)/II and the proportion of benzene-d1 in the benzene fraction obtained from the photoreactions of DMA-d6 with halobenzenes. From the kinetic and fluorescence data, an exciplex mechanism was suggested for the photoreactions with chlorobenzene and bromobenzene, and a direct electron transfer mechanism in the case of iodobenzene.
  • Tadashi Sato, Takeshi Inoue, Koichi Yamamoto
    1972 Volume 45 Issue 4 Pages 1176-1179
    Published: 1972
    Released: March 27, 2006
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    The photochemical reaction of mesityl oxide oxime was investigated. In protic solvents, the reaction via oxaziridine proceeded, while in aprotic solvents, syn-anti isomerization was the main reaction pattern. A cyclobutanol formation, which is a new type of reaction in the oxime system, was observed. The photochemical reactions on some other ketoximes and their derivatives were also investigated.
  • Teng-Yueh Chen, Mu-Huang Hung, Po-Tau Chen, Masaki Ohta
    1972 Volume 45 Issue 4 Pages 1179-1183
    Published: 1972
    Released: March 27, 2006
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    1-t-Butyl-3-amino, 1-t-butyl-3-aminomethyl-, and 1-t-butyl-2-aminomethylazetidine were prepared by the ammonolysis of 1-t-butyl-3-azetidinyl tosylate, and by the reduction of 1-t-butyl-3-cyano, and 1-t-butyl-2-cyanoazetidine respectively. In the deamination, both of the first two azetidines gave only the corresponding alcohols, 1-t-butyl-3-azetidinol and 1-t-butyl-3-hydroxymethylazetidine, while the last one was found to afford two products, 1-t-butyl-2-hydroxymethylazetidine and 1-t-butyl-3-hydroxypyrrolidine. The deamination products were identified as the corresponding acetates.
  • Kuniyuki Takahashi, Akihisa Miyake, Go Hata
    1972 Volume 45 Issue 4 Pages 1183-1191
    Published: 1972
    Released: March 27, 2006
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    Active methylene compounds, such as acetylacetone and ethyl acetoacetate, reacted with 1,3-butadiene in the presence of palladium-diphosphine complex catalysts to yield two 1 : 1 adducts, 1 and 2. Primary and secondary amines also afforded two 1 : 1 adducts, 10 and 11. Isoprene, 1,3-pentadiene, and 2,4-hexadiene also reacted with the active methylene compounds and the amines in a manner similar to that of 1,3-butadiene. The most effective and easily available catalyst is the combination of PdBr2(Ph2PCH2CH2PPh2)2 and sodium phenoxide.
  • Kunio Okamoto, Kôichi Matsubara, Tomomi Kinoshita
    1972 Volume 45 Issue 4 Pages 1191-1198
    Published: 1972
    Released: March 27, 2006
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    Adamantyl derivatives, the bridgehead substrates, have been chosen as the reference compounds in the assessment of the ionizing power of phenolic solvents in the ,SN1-type solvolysis. The SN1-phenolyses of 1-adamantyl chloride, bromide, and p-toluenesulfonate have been studied at several temperatures in binary mixtures of phenol with benzene; the enthalpies and entropies of activation have been calculated. Phenolysis has also been made on t-butyl chloride in order to estimate the Grunwald-Winstein Y values for the phenol-benzene solvents. The solvolysis rates of 1-adamantyl compounds, including the literature values, have been correlated with the Y values and also with the dielectric constants ((D−1)⁄(2D+1)). A significant deviation is found for the phenolic solvents in both correlations; this deviation is discussed in terms of the electrophilic assistance by hydrogen-bonding of the phenolic solvents to the leaving group. The isolated phenolysis products have been characterized as 1-adamantyl phenyl ether, o-, and p-1-adamantylphenols. The product compositions for the reactions of the ion-pair intermediate with the phenol molecule and with the phenoxide ion have been estimated on the basis of the variation in the overall product compositions, caused by the increase in the concentrations of the added phenoxide or amine.
  • Yasuhide Yukawa, Yuho Tsuno, Masami Sawada
    1972 Volume 45 Issue 4 Pages 1198-1205
    Published: 1972
    Released: March 27, 2006
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    The rates of the alkaline hydrolyses of 24 m- and p-substituted-benzyl benzoates were measured in 70% (v/v) aqueous acetone at 25°C. The given set of σ0 constants was precisely identical with our standard set derived from m- and p-substituted ethyl phenylacetates. The general utility of σ0 constants is demonstrated for unexalted and exalted resonance reactivities as the reference scale in our LArSR equation:
    logkk0=ρ(σ0+r+Δ\barσ\overset+R+rΔ\barσ\overset−R)
  • Masami Sawada, Yuho Tsuno, Yasuhide Yukawa
    1972 Volume 45 Issue 4 Pages 1206-1209
    Published: 1972
    Released: March 27, 2006
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    The rates of the alkaline hydrolysis of 9 polynuclear arylcarbinyl benzoates were measured in 70% (v/v) aqueous acetone at 25°C. The new set of σ0 values for polynuclear aryls was obtained, using the ρm value established by the hydrolysis of m- and p-substituted-benzyl benzoates. In the present reaction, it is possible to assume that the peri-hydrogen steric effect is practically absent, bacause o-tolyl derivative gives a σ0 a value comparable with that of p-tolyl, and 1-naphthyl with that of 2-naphthyl. The set thus obtained can be successfully described in terms of two components; self-atom polarizability and Streitwieser’s inductive index, ∑rij−1.
  • Yasuhide Yukawa, Yuho Tsuno, Masami Sawada
    1972 Volume 45 Issue 4 Pages 1210-1216
    Published: 1972
    Released: March 27, 2006
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    The basicities of nine polynuclear aryl methyl ketones have been determined spectrophotometrically in various aqueous sulfuric acid solutions. The electronic effects of unhindered polynuclear aryls on pKBH+ can be successfully correlated with our LArSR equation,
    logkk0=ρ(σ0+\barσ\overset+R),
    using ρ and r values established from meta- and para-substituted acetophenones. The applicability of this equation to polynuclear aryls is also shown for some other electrophilic reactivities. The Δ\barσ\overset+R parameters for polynuclear aryls are derived empirically from the solvolysis of α-arylethyl chlorides; these show a good linearity with the theoretical reactivity indices of the localization energies.
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