Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 55 , Issue 8
Showing 1-50 articles out of 81 articles from the selected issue
  • Kazuaki Harata
    1982 Volume 55 Issue 8 Pages 2315-2320
    Published: 1982
    Released: June 27, 2006
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    The crystal structure of β-cyclodextrin–1,4-diazabicyclo[2.2.2]octane complex tridecahydrate was determined by the X-ray method. The crystal is monoclinic with the space group P21, Z=2, a=15.395(2), b=16.598(1), c=15.441(2) Å, and β=117.35(1)°. The structure was solved by inspection of a Patterson map and a trial-and-error method combined with the rigid-body least-squares technique and refined by the block-diagonal least-squares method to the final R-value of 0.048 for 5649 reflections (sinθ⁄λ<0.61). The β-cyclodextrin molecule is in the shape of a distorted and truncated heptagonal pyramid. Two of seven primary hydroxyl groups are in a gauche-trans conformation, the others being in a gauche-gauche conformation. Secondary hydroxyl groups form intramolecular hydrogen bonds between adjacent glucose residues. The guest 1,4-diazabicyclo[2.2.2]octane is almost fully included in the cavity of β-cyclodextrin. Its methylene groups are in van der Waals contact with the methine groups and the glycosidic oxygen atoms at the interior surface of β-cyclodextrin, while two nitrogen atoms form hydrogen bonds with a water molecule and a secondary hydroxyl group of the neighboring β-cyclodextrin. β-Cyclodextrin molecules are arranged nearly parallel to the crystallographic ac plane to form a corrugated sheet of molecular layer. All of the thirteen water molecules fill vacant spaces between the molecular layers, forming a hydrogen-bond network in the crystal.
  • Toshio Furuya, Sumio Iwanami, Akio Takenaka, Yoshio Sasada
    1982 Volume 55 Issue 8 Pages 2321-2326
    Published: 1982
    Released: June 27, 2006
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    The crystal and molecular structure of the title compound has been determined by the X-ray diffraction method. The crystal is monoclinic, space group P21/c, a=11.694(1) Å, b=12.117(1) Å, c=14.482(1) Å, β=100.01(1)°, and Z=4. The structure was solved by the direct method and refined by a block-diagonal least-squares procedure to a final R value of 0.082. An intramolecular hydrogen bond between the amide nitrogen and the methoxyl oxygen atoms forms a new six-membered ring fused with the benzene ring. Structural features are discussed in relation to neuroleptic activity.
  • Michiko Konno, Shi-aki Hyodo, Sei-ichiro Iijima
    1982 Volume 55 Issue 8 Pages 2327-2335
    Published: 1982
    Released: June 27, 2006
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    The crystal structure of 1′,1'″-dipropylbiferrocenium (PrFcFcPr)+I3, which shows averaged-valence irons at 298 K and trapped-valence irons at 110 K, was determined by X-ray diffraction. The crystal at 298 K is triclinic, space group P\bar1, a=8.5148(8), b=8.5482(5), and c=10.9032(13) Å, α=89.546(9), β=115.582(9), and γ=108.488(7)°, U=671.10(9) Å3, and Z=1. The crystal at 110 K is triclinic, space group P1, a=8.431(2), b=8.478(2), and c=10.816(3) Å, α=88.58(3), β=117.39(2), and γ=108.65(2)°, U=643.4(3) Å3, and Z=1. Structures were refined to R=0.042 at 298 K and R=0.050 at 110 K. At 298 K cation (PrFcFcPr)+ sits on the symmetry center and the two Fc units are crystallographically equivalent, whereas at 110 K the symmetry center is lost and ferrocene-like and ferrocenium-like Fc units are distinguished. A three-dimensional hydrogen-bond network is clearly found between the cation and iodine atoms at 110 K, in contrast to the result at 298 K. Infrared spectra of 1′,1'″-diethyl- and 1′,1'″-dipropylbiferrocenium+I3 and μ-(as-indacenyl)-bis(cyclopentadienyliron)+I30.5I2 salts measured at 294 and 78 K indicate that a remarkable change in peak intensity is observed at 680 and 1525 cm−1 in the dialkyl salts, whereas no change is found in the remainder.
  • Kunio Furusawa, Satoshi Yamashita
    1982 Volume 55 Issue 8 Pages 2336-2340
    Published: 1982
    Released: June 27, 2006
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    The phase diagrams of monodisperse latices were constructed under the various conditions. The variable of the phase diagrams, the particle size, the surface charge densities of the latices, the counter-ion valences, and the medium temperature were taken up. The results, especially, the coexistent/ordered boundary curves were analysed in terms of the closed packing of the effective particle volumes which consisted of the latex particles which were surrounded by the electrical double layer. The value of 1.5 kT ergs of electrical repulsion, when used as a criterion in the DLVO potential to back-calculate the weight fraction of solid contents as a function of KCl concentration, yields a curve that is very similar to the experimental boundary curve. The same agreement was found in the curves mapped out for the other latices with a different particle size and a different surface charge density using KCl as an electrolyte. In the boundary curve constructed using MgCl2, however, the agreement with the analyses was not enough where the divalent cation would be adsorbed preferentially on their surfaces as a Stern layer charge. The temperature effect could be reasonably explained by the same procedure.
  • Takashi Sumiyoshi, Sadashi Sawamura, Yoshio Koshikawa, Meiseki Katayam ...
    1982 Volume 55 Issue 8 Pages 2341-2346
    Published: 1982
    Released: June 27, 2006
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    Formation and decay of transient species produced in pure liquid carbon tetrachloride by ionizing radiation were studied by using a stroboscopic pulse radiolysis technique in the time region 35–350 ps. Optical absorption spectra show two principal bands. One narrow band centered at 325 nm, which is formed during each fine structure electron pulse and decayed after pulse with t1⁄2=6.5 ns, is attributed to CCl4+ cation. The other broad band centered at 470 nm built up after electron pulse is assigned to (CCl4+·Cl). A consideration on effects of cation scavengers on these bands furnishes a support for the above assignment.
  • Takashi Sumiyoshi, Nobuyuki Miura, Masayuki Aikawa, Meiseki Katayama
    1982 Volume 55 Issue 8 Pages 2347-2351
    Published: 1982
    Released: June 27, 2006
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    Reaction mechanisms between methyl methylthiomethyl sulfoxide (MTMSO) and hydrated electron (eaq) or hydroxyl radical (OH· radical) have been studied in aqueous solutions with various pH values by means of pulse radiolysis technique. The acid and basic components of equilibrium
    (Remark: Graphics omitted.)
    and
    (Remark: Graphics omitted.)
    are formed for the reaction of eaq+CH3SCH2SOCH3 and OH· +CH3SCH2SOCH3, respectively. The pKa values of the respective equilibrium are 10 and 9. The anion (I) and (II) have absorption maxima at 375 nm and 360 nm, respectively. The sulfinic acid CH3SCH2SO2 is also formed in the reaction of CH3SCH2SOCH3+OH·. The rate constants have been determined to be k(eaq+MTMSO)=1.3×108 M−1 s−1 and k(OH· +MTMSO)=3.1×109 M−1 s−1 (1 M=1 mol dm−3). Relative reactivities of OH· radical with thio-methyl bond and sulfinyl group are also discussed.
  • Masayuki Aikawa, Takashi Sumiyoshi, Nobuyuki Miura, Meiseki Katayama
    1982 Volume 55 Issue 8 Pages 2352-2355
    Published: 1982
    Released: June 27, 2006
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    The dynamics of hydrated electrons generated by pulsed electron beams was studied for micellar systems with a series of halogenated naphthalenes as substrates exclusively dissolved in micellar phase. Time behavior of absorption for hydrated electrons, displayed as a curve consisting of two exponential decays, affords evidence that two different routes exist in advance of dissociative electron attachement: 1) direct penetration of electrons through micellar phase with substrates, and 2) migration of hydrated electrons between micells in the absence and presence of substrates, prior to the penetration of electrons into the reactive center in the micelle. Electrostatic interaction of hydrated electrons with positively charged surface of micelles is also discussed.
  • Katsuma Hiraki, Naoyuki Ochi, Tsuneyuki Kitamura, Yoko Sasada, Sumio S ...
    1982 Volume 55 Issue 8 Pages 2356-2363
    Published: 1982
    Released: June 27, 2006
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    A hydridoruthenium(II) complex [RuClH(CO)(PPh3)3] reacted easily with acrylonitrile and fumaronitrile to give chloro-bridged binuclear (1-cyanoethyl)ruthenium(II) complexes, [{Ru(MeCHCN)Cl(CO)(PPh3)2}2] (2) and [{Ru(NCCH2CHCN)Cl(CO)(PPh3)2}2], respectively. Complex 2 reacted with 4-picoline (pic), Na[BHPz3] (Pz=1-pyrazolyl), Na[BPz4], and Na[Et2NCS2]·3H2O to afford the corresponding (1-cyanoethyl)ruthenium(II) complexes, [{Ru(MeCHCN)Cl(CO)(pic)(PPh3)}2] (3), [Ru(MeCHCN)(BHPz3)(CO)(PPh3)] (accompanied by a small amount of [Ru2(MeCHCN)2Cl(BHPz3)(CO)2(PPh3)4]), [Ru2(MeCHCN)2Cl(BPz4)(CO)2(PPh3)2], and Na[Ru(MeCHCN)Cl(Et2NCS2)(CO)(PPh3)], respectively. Complex 3 reacted with thallium(I) acetylacetonate [Tl(acac)], resulting in the formation of [{Ru(MeCHCN)(acac)(CO)(PPh3)}2] and [Ru(MeCHCN)(acac)(CO)(pic)(PPh3)]. These new complexes were characterized by means of elemental analysis and spectroscopic data. The diastereoisomerism was also discussed as regards these (1-cyanoethyl)ruthenium(II) complexes.
  • Norikazu Ueyama, Kazuko Sasaki, Michio Nakata, Akira Nakamura
    1982 Volume 55 Issue 8 Pages 2364-2370
    Published: 1982
    Released: June 27, 2006
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    Cysteine-containing peptide (pep) complexes of Pd(II) have been synthesized and their structures in organic solvents such as dimethyl sulfoxide (Me2SO) and N,N-dimethylformamide (DMF) were examined by use of 1H-, 13CNMR, visible, and CD spectroscopies. In all cases of the Pd(II) complexes, only the thiolato group of the peptides coordinates to the metal. Upon mixing [PdCl4]2− and the peptide, a trans(S) isomer [PdCl2(pep)2]2− immediately forms, which gradually isomerizes to the cis(S) isomer at 20 °C in DMF. The reactivity of Pd(II)–S bonds in these complexes was examined by addition of 2,2′-bipyridyl, 2-mercaptoethanol, or 3,4-toluenedithiol.
  • Mamoru Shimoi, Akira Ouchi, Takashi Uehiro, Yukichi Yoshino, Shoichi S ...
    1982 Volume 55 Issue 8 Pages 2371-2377
    Published: 1982
    Released: June 27, 2006
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    Several amine or phosphine adducts of bis (O,O′-dialkyl dithiophosphato)cobalt(II), which were hardly oxidized in air at room temperature, were obtained as crystalline solids. The crystal and molecular structure of one adduct, Co(Me2dtp)2(triphenylphosphine) (Me2dtp=O,O′-dimethyl dithiophosphato group), was determined by means of the X-ray diffraction method. The crystal is monoclinic: space group P21/n, a=26.712(4), b=9.495(1), c=11.180(5) Å, β=95.43(3)°, Z=4, Dx=1.495, Dm=1.45 g cm−3, μ(Mo Kα)=1.17 mm−1, and the final R value obtained is 0.062 for 4466 observed reflections. The coordinated atoms around the cobalt atom are in a trigonal bipyramidal configuration. The approximate first formation constants of the adducts, K=[Co(II)(R2dtp)2·X]/{[Co(II)(R2dtp)2][X]} (R=alkyl group, and X=donor) in solution, were obtained by means of the spectrophotometric as well as the NMR technique.
  • Tadashi Iwachido, Masayoshi Minami, Hirohiko Naito, Kyoji Tôei
    1982 Volume 55 Issue 8 Pages 2378-2382
    Published: 1982
    Released: June 27, 2006
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    The distribution ratios, D,of potassium between an aqueous KCl solution and 57 organic solvents (8 alcohols, 12 ketones, 6 esters, 3 ethers, and 28 hydrocarbons(24 halo- and 2 nitro-substituted and 2 unsubstituted)) were determined in the presence or in the absence of L. The presence of L markedly enhances the extractability of potassium when the halogenated hydrocarbon solvents are used, but only a slight enhancement can be observed for the oxygen-containing solvents. Among the properties showing good correlations with D, Hansen’s three-dimensional solubility parameters and Dimroth’s ET values are most satisfactory for their applicability to a wide variety of solvents.
  • Shuhei Fujinami, Kenshi Tsuji, Muraji Shibata
    1982 Volume 55 Issue 8 Pages 2383-2389
    Published: 1982
    Released: June 27, 2006
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    The crystal field model of d-d optical activity has been applied to complexes with cis(N)-[Co(N)2(O)4] and cis(O)-[Co(N)4(O)2]+ chromophores, and the Cotton signs of these complexes have been predicted. The model has shown that the Cotton signs in CD spectra of the complexes depend upon: 1) the energy difference between Ega and A2g states, 2) the coordination angle in a bidentate chelate, and 3) the effective charge of the ligating atoms. The CD spectral difference between an optically active carbonato complex and the corresponding diaqua complex derived from the carbonato complex has been understood in terms of the effective charge of the ligating O atoms.
  • Keiji Akamatsu, Takashi Komorita, Yoichi Shimura
    1982 Volume 55 Issue 8 Pages 2390-2395
    Published: 1982
    Released: June 27, 2006
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    Glycinato, L-alaninato, ethylenediamine, N,N-dimethylethylenediamine, (R)-propylenediamine, (R,R)-1,2-cyclohexanediamine and meso-2,3-butanediamine cobalt(III) complexes of a tripodlike ligand, N-(2-aminoethyl)iminodiacetate have been prepared. The geometrical configurations are assigned on the basis of their absorption, circular dichroism, and 1H-NMR spectra. The trans(O) isomer of meso-2,3-butanediamine complex is optically resolved and the relationship between the absolute configurations of the chiral 1,2-diamine complexes and their circular dichroism is discussed.
  • Junko Motonaka, Sanae Ikeda, Nobuyuki Tanaka
    1982 Volume 55 Issue 8 Pages 2396-2399
    Published: 1982
    Released: June 27, 2006
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    A rapid method has been established for determination of mixtures of hydrazine and hydroxylamine by potentiometric titration using an iodide ion-selective electrode. Accurate values are obtainable when nitric acid is added to the sample solution. A recommended procedure is proposed in which the sum of hydrazine and hydroxylamine is titrated with an aliquot of sample solution and another aliquot is titrated to the end point for hydrazine after hydroxylamine has been decomposed with nitric acid. Hydrazine and hydroxylamine in mixture can be determined in the concentration range of 0.01–0.5 mmol/dm3. The best result, with relative error and relative standard deviation both of less than 0.7%, may be obtained on 0.5 mmol/dm3 hydrazine and hydroxylamine.
  • Michio Nakamura, Hisashi Okawa, Takahiko Inazu, Sigeo Kida
    1982 Volume 55 Issue 8 Pages 2400-2403
    Published: 1982
    Released: June 27, 2006
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    Cobalt(III) mixed-chelates, Co(SB)(l-moba), containing a salen-type Schiff base (SB) and 1-l-menthyloxy-3-benzoylacetone (H(l-moba)) have been synthesized, where H2salen stands for N,N′-disalicylideneethylenediamine. These complexes were shown to have a cis-β-octahedral structure, based on electronic and infrared spectra. They showed circular dichroism in the visible region, demonstrating an induction of an asymmetry around the metal ion. On the basis of NMR and CD spectra and in comparison with the CD spectrum of Λ-Co(sal-(S, S)-ch)(bazc), it was shown that the Co(SB) (l-moba) complexes prefer the Λ-cis1-configuration. The reaction of racemic N,N′-disalicylidene-trans-1,2-cyclohexanediaminatocobalt(II) (Co(salch)) and racemic N,N′-disalicylidene-1,2-propanediaminatocobalt(II) (Co(salpn)) with H(l-moba) in a 2 : 1 mole ratio yielded Λ-cis1-Co(sal-(S, S)-ch)(l-moba) and Λ-cis1-Co(sal-(R)-pn)(l-moba), respectively, as amain species. The stereoselectivity in the present complexes has been discussed in terms of the inter-ligand, hydrophobic CH/π-interaction which may occur between the l-menthyl group and an aromatic ring of the Schiff bases.
  • Ichiro Murase, Masao Hatano, Masahiko Tanaka, Shigehiro Ueno, Hisashi ...
    1982 Volume 55 Issue 8 Pages 2404-2408
    Published: 1982
    Released: June 27, 2006
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    Dihydrochloride of a binucleating ligand, 1,5-diamino-3-pentanol (Hdpl·2HCl) has been synthesized by a new method in a high yield (>70%). This ligand forms 1 : 1 complexes with copper(II), Cu(dpl)X(X=BF4, ClO4, NO3, and Cl(H2O)). The cryomagnetic study of the copper complexes has shown that they are binuclear, and a strong antiferromagnetic interaction is operating between two copper ions. The binuclear structure seems to be quite stable even in aqueous solution. The 1 : 1 complex with nickel(II) was also isolated as tetraphenylborate, which was essentially diamagnetic. A planar binuclear structure similar to the copper complexes was assumed for this complex. Its absorption band at 29.8×103 cm−1 (ε=160) was attributed to the charge transfer transition from the bridging oxygen to the nickel similarly to the bands in the 25–29×103 cm−1 region usually observed for alkoxo-oxygen bridged binuclear copper(II) complexes. Some 2 : 1 copper(II)–dpl complexes have also been synthesized and characterized as binuclear complexes. 1,5-Bis(dimethylamino)-3-pentanol has been synthesized, and its 2 : 1 copper(II) complexes have been isolated.
  • Tomoya Sakai, Masahiko Ishizaki, Masafumi Goto
    1982 Volume 55 Issue 8 Pages 2409-2414
    Published: 1982
    Released: June 27, 2006
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    The rapid aldol addition of formaldehyde to 2-hydroxyacetophenone (HAP), an efficient accelerator for formose formation, took place to yield addition products of HAP with one and two molecules of formaldehyde at 35 °C in an aqueous 40% methanol mixture of formaldehyde, HAP, and Ca(OH)2. No further addition product with more than two molecules of formaldehyde attached to HAP was detected throughout the reaction. On the contrary, benzaldehyde and benzoic acid were formed, accompanied by formose sugars. The initial molar amount of HAP corresponded to the sum of the compounds substituted with the phenyl group including benzaldehyde and benzoic acid. The retro-aldol reaction of the HAP derivatives is likely to be involved in the overall reaction to yield glycolaldehyde or trioses, which are good accelerators for formose formation.
  • Tadashi Kozuka
    1982 Volume 55 Issue 8 Pages 2415-2423
    Published: 1982
    Released: June 27, 2006
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    A series of p-benzoquinones having an ester functional group in the α position of alkyl side chains was prepared. Irradiation of these quinones, except for methyl 3-methyl-2-(4-methyl-3,6-dioxo-1,4-cyclohexadienyl)-butyrate (3e), rapidly gave methyl 3-substituted 2,3-dihydro-5-hydroxybenzofuran-2-carboxylate in fairly good yields, and it was found that rearrangement of the side chain occurred concomitantly. Photolysis of quinone 3e afforded methyl 2-(2,5-dihydroxy-4-methylphenyl)-3-methyl-3-butenoate as the major product. An intermediate was postulated to account for the isolated photoproduct.
  • Nobukatsu Katsui, Fujio Yagihashi, Akio Murai, Tadashi Masamune
    1982 Volume 55 Issue 8 Pages 2424-2427
    Published: 1982
    Released: June 27, 2006
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    The isolation and structure elucidation of the title spirovetivane sesquiterpenes, stress metabolites produced in diseased potato tubers, are described.
  • Nobukatsu Katsui, Fujio Yagihashi, Akio Murai, Tadashi Masamune
    1982 Volume 55 Issue 8 Pages 2428-2433
    Published: 1982
    Released: June 27, 2006
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    The isolation and structure elucidation of the title valencane sesquiterpene, a stress metabolite produced in diseased potato tubers, are described.
  • Akira Kasahara, Taeko Izumi, Iwao Shimizu, Masahiro Satou, Takao Katou
    1982 Volume 55 Issue 8 Pages 2434-2440
    Published: 1982
    Released: June 27, 2006
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    [2]Paracyclo[2]paracyclo[2](1,8)naphthalenophan-9-ene-1,17-diyne, [0]paracyclo[2]paracyclo[0](5,6)acenaphthenophan-7-ene, and [2]paracyclo[2]paracyclo[2](5,6)acenaphthenophan-9-ene-1,17-diyne, were synthesized by intramolecular reductive coupling reaction of the corresponding carbonyl compounds with low-valent titanium reagent. The structures of the compounds were elucidated by NMR analyses, and the transannular π-electronic interactions between two benzene rings were examined on the basis of electronic spectra.
  • Yoshihisa Watanabe, Tetsuo Ohta, Yasushi Tsuji
    1982 Volume 55 Issue 8 Pages 2441-2444
    Published: 1982
    Released: June 27, 2006
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    Carbonyl compounds were hydrogenated to the corresponding alcohols in excellent yields using formic acid with a ruthenium complex at 125 °C for 3 h. 2-Propanone was reduced to 2-propanol by RuCl2(PPh3)3–HCOOH system in 94% yield with 98% selectivity. 3-Pentanone, cyclohexanone, acetophenone, and propiophenone were hydrogenated to the corresponding alcohols in 86, 78, 84, and 86% yields respectively. The ketone having the bulkier alkyl groups showed lower reactivity. The catalytic activity was found to decrease in the order RuCl2(PPh3)3, RuHCl(PPh3)3, RuHCl(CO)(PPh3)3, and RuH2(PPh3)4.
  • Yoshihisa Watanabe, Naoki Suzuki, Yasushi Tsuji
    1982 Volume 55 Issue 8 Pages 2445-2449
    Published: 1982
    Released: June 27, 2006
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    The Catalytic N-heterocyclization of aminoarenes and dinitroarenes using aliphatic n-C3–C5 aldehydes was carried out at 180 °C under the pressure of carbon monoxide (70 atm at room temperature) in the presence of RhCl(PPh3)3 and PdCl2 as a binary catalyst system. The reaction of p-nitroaniline with propanal, butanal, and pentanal gave 3,8-diethyl-2,9-dimethyl-4,7-phenanthroline, 2,9-diethyl-3,8-dipropyl-4,7-phenanthroline, and 3,8-dibutyl-2,9-dipropyl-4,7-phenantroline in 43, 57, and 54% yields respectively. On the other hand, m-nitroaniline and o-nitroaniline gave 1,7-phenanthroline and imidazole derivatives in rather low yields (21 and 24%) under the reaction conditions employed.
  • Tomio Shimizu, Yoshiyuki Hayashi, Yoshitaka Kitora, Kazuhiro Teramura
    1982 Volume 55 Issue 8 Pages 2450-2455
    Published: 1982
    Released: June 27, 2006
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    2-(3-Aryl-2-propenyloxy)benzaldehyde (or 1-naphthaldehyde) arylhydrazones undergo an intramolecular cycloaddition reaction via their 1,3-dipolar tautomers, azomethine imines, to the alkenyl group. Initial cycloadducts were converted to dehydrogenated compounds under the reaction conditions. On the other hand, introduction of cyano or ethoxycarbonyl groups instead of the aryl group into 3-position of the ortho propenyloxy group gave 3-cyanomethyl-4-chromanone arylhydrazones or the corresponding ethoxycarbonyl derivatives, respectively. The formation of these hydrazones was interpreted in terms of intramolecular ene reaction. The course of the reactions depends on the nature of the alkenyl substituents.
  • Tomio Shimizu, Yoshiyuki Hayashi, Susumu Ishikawa, Kazuhiro Teramura
    1982 Volume 55 Issue 8 Pages 2456-2459
    Published: 1982
    Released: June 27, 2006
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    The reaction of the arylhydrazones of some 2-(alkenyloxy)benzaldehydes(or 1-naphthaldehydes) with Pb(OAc)4 leads, via the nitrilimine intermediates, to intramolecular 1,3-dipolar cycloadducts, 3-substituted 2-aryl-2,3,3a,4-tetrahydro[1]benzopyrano(or naphtho[1′,2′:5,6]pyrano)[4,3-c]pyrazoles, in 10–80% yields. In the presence of an excess of Pb(OAc)4, these cycloadducts were dehydrogenated to 3-substituted 2-aryl-2,4-dihydro[1]benzopyrano(or naphtho[1′,2′:5,6]pyrano)[4,3-c]pyrazoles. In the presence of a large excess of Pb(OAc)4, some of the pyrazoles were acetoxylated to give the corresponding 4-acetoxypyrazoles. The effect of substituents of the alkenyl group on reactivity of the reaction was interpreted in terms of the frontier molecular orbital (FMO) theory.
  • Mitsuhiro Koden, Shunsuke Takenaka, Shigekazu Kusabayashi
    1982 Volume 55 Issue 8 Pages 2460-2463
    Published: 1982
    Released: June 27, 2006
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    The thermal properties of cholesteryl esters of substituted benzoylbenzoic acids were examined. The substituent effects on the thermal stability of the chloesteric phase of these esters are quite striking. For cholesteryl 4-(4′-substituted benzoyl)benzoates, the Ch-I transition temperatures are slightly influenced by an electronic effect of the substituents, because the bond direction of the substituents is tilted with respect to the long molecular axis. For cholesteryl 4-(3′-substituted benzoyl)benzoates and cholesteryl 3-(4′-substituted benzoyl)benzoates, the Ch-I transition temperatures are influenced by the polarizability anisotropy of the terminal phenyl ring, which probably gives rise to a change in the ratio of the number of more-linear isomers to the number of less-linear isomers. For cholesteryl 4-(2′-substituted benzoyl)benzoates, the substituents increase the angle between the two phenyl rings, i.e., the thickness of the benzophenone moiety, due to the repulsive interaction between the substituent(s) and ortho-hydrogens of the other phenyl ring, and therefore decrease the Ch-I transition temperature largely.
  • Noritaka Abe, Tarozaemon Nishiwaki, Kotaro Ikeda
    1982 Volume 55 Issue 8 Pages 2464-2469
    Published: 1982
    Released: June 27, 2006
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    Cycloaddition of 5-aryl-3-methylimidazo[5,1-b]thiazoles with dialkyl acetylenedicarboxylate in an aprotic nonpolar solvent gives a number of products including epimeric thiazolo[2,3-c]benzimidazoles (3 and 4) [1:2-cycloadducts], epimeric 5,10b-ethenothiazolo[3′,2′:3,4]imidazo[1,5-a]-pyridines (5 and 6) [1:3-cycloadducts], and thiazolo[3′,2′:3,4]imidazo[1,2-a]pyridines [1:3-adducts]. At higher temperature, formation of the 1:2-cycloadducts is favored over the 1:3-adducts, whereas the latter predominates at room temperature. In an aprotic polar medium, the 1:3-cycloadducts (5 and 6) and tetraalkyl 6-arylpyridine-2,3,4,5-tetracarboxylates are substantially produced. Epimerization of 3 and 4 has been found to compete well with fragmentation to 4H-1,4-benzothiazine.
  • Koichi Komatsu, Katsuhisa Masumoto, Yoshinori Waki, Kunio Okamoto
    1982 Volume 55 Issue 8 Pages 2470-2479
    Published: 1982
    Released: June 27, 2006
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    A series of polymethylenebis(diphenylcyclopropenium) dications with the polymethylene chain of one to six carbons (4n=1–6) were synthesized and characterized by spectral and analytical means. Among the dications 4n=3–6 which were isolated as perchlorates, 4n=3 was shown by the pKR+ measurements to be destabilized by 1.3 pK units as compared with 4n=4–6. The values of reduction potential exhibited the same tendency. The chromium(II) ion reduction of 4n=6, a representative dication, afforded a polymeric material containing a hexylbenzene unit. The dication 4n=2 was isolable only as a complex salt with SbCl6 and Cl: the conventional hydride abstraction from 1,2-dicyclopropenylethane using trityl perchlorate resulted in rearrangements affording 4,9,10-triphenylphenanthrene and the unknown monocation C32H25+ containing the tropylium ring. A possible mechanism for these rearrangements is presented. On the other hand, the dication 4n=1 was observable only in a highly acidic solution due to the ready deprotonation yielding a new fully conjugated monocation 17. This cation, characterized by remarkable stability (pKR+ 8.9 in 50% aq acetonitrile), is formally represented as a triafulvene with a cyclopropenium ring substituted at the 4-position, but is shown to have a partially polarized electronic structure by 13C NMR spectroscopy.
  • Hideyo Yamada, Yasuo Wada, Shigeo Tanimoto, Masaya Okano
    1982 Volume 55 Issue 8 Pages 2480-2483
    Published: 1982
    Released: June 27, 2006
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    The reaction of aliphatic isocyanides with bromine or chlorine in primary alcohols, followed by hydrolysis, afforded the corresponding carbamates in moderate yields, together with various amounts of amines. Bromine was superior to chlorine as a halogen source for the formation of carbamates. unexpectedly, the addition of HgCl2 resulted in a decrease in the carbamate yield. When N-halosuccinimides were used in the place of halogens, an additional formation of the succinimide-incorporated product was observed to some extent.
  • Shigeru Oae, Toshikazu Takata, Yong Hae Kim
    1982 Volume 55 Issue 8 Pages 2484-2494
    Published: 1982
    Released: June 27, 2006
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    Oxidation of an unsymmetrical disulfide, methyl phenyl disulfide, with peroxy acids takes place mainly at more electron-rich sulfur atom to form thiosulfinic S-ester at the first stage, while oxidation of unsymmetrical thiosulfinic S-ester with peroxy acids gives usually four thiosulfonic S-esters, together with sulfinic and sulfonic acids, further oxidation products. Oxidation of S-methyl benzenethiosulfinate 6 affords, as one of the products, S-phenyl methanethiosulfonate 11, in which the original sulfinyl oxygen is brought into methanesulfonyl group. A small amount of S-phenyl benzenethiosulfonate 9 (or benzenesulfonic acid 15) is obtained in the oxidation of S-phenyl methanethiosulfinate 7. 18O-Label of the starting thiosulfinic S-ester 6 was found to be incorporated to some extents into all four products, i.e. 811, while a part of 18O-label of S-phenyl methanethiosulfinate 7 was also observed in S-phenyl benzenethiosulfonate 9 and benzenesulfonic acid 15, although most of 18O-label of 7 was incorporated into S-phenyl methanethiosulfonate 11. Thiosulfinic S-esters are stable and do not undergo disproportionation and 18O-exchange under the conditions. These observations suggest the formation of α-disulfoxide as an intermediate in the oxidation of thiosulfinic S-ester to thiosulfonic S-ester, especially in the oxidation of 6, although no peak corresponding to α-disulfoxide was observed directly in the NMR spectra taken during the oxidations of a few thiosulfinic S-esters with peroxy acids. Mechanism of the oxidation is discussed.
  • Yukimasa Terada, Shosuke Yamamura
    1982 Volume 55 Issue 8 Pages 2495-2499
    Published: 1982
    Released: June 27, 2006
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    Molecular mechanics calculations were successfully carried out to evaluate relative stabilities of each conformation of germacrenes in their ground states and transition states. In the calculation of such a transition state model as shown in Scheme 1, the parameters for partial bonds were taken as mean values of those for a reactant and a product. Thus, the calculation results on each transition state model indicate that the elemenes are formed from the corresponding germacrenes through the most stable transition state (CC), regardless of the most stable conformers in ground state. Calculations were also carried out on ground and transition states of acoragermacrone and isoacoragermacrone, both of which have an α,β-unsaturated carbonyl system. The calculation results on each transition state model indicate that shyobunone (5) and epishyobunone (6) both are formed from acoragermacrone through the corresponding transition states [5 from CC; 6 from C′C′ and C′T] in relative ratio (5/6=87/13) which is in good agreement with that of the experimental result (5/6=84/16). In the case of isoacoragermacrone, molecular mechanics calculations indicate that the preisocalamendiol-type transition state model is more favorable than the models corresponding to the Cope rearrangement products.
  • Seiji Yamaguchi, Seizo Kondo, Keiko Shimokawa, Osamu Inoue, Michiko Sa ...
    1982 Volume 55 Issue 8 Pages 2500-2503
    Published: 1982
    Released: June 27, 2006
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    2-Isopropenyl-2,3-dihydrobenzofuran was effectively prepared by two new methods. Fomannoxin and 5-acetyl-2-[1-(hydroxymethyl)vinyl]-2,3-dihydrobenzofuran were synthesized from 2-isopropenyl-2,3-dihydrobenzofuran, while anodendroic acid was synthesized from 2-(1-hydroxy-1-methylethyl)-2,3-dihydrobenzofuran.
  • Takashi Ando, Junko Yamawaki, Takehiko Kawate, Shinjiro Sumi, Terukiyo ...
    1982 Volume 55 Issue 8 Pages 2504-2507
    Published: 1982
    Released: June 27, 2006
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    The effectiveness of alkali metal fluorides impregnated on alumina as a reagent for promoting alkylation was optimized with respect to the metal cation, the amount of impregnation, and the reaction solvent. Potassium or caesium fluoride on alumina in acetonitrile or 1,2-dimethoxyethane was concluded to be the best reaction system for general use. O-Alkylation of substituted phenols, primary and secondary alcohols, and a glycol was carried out mostly in good yields under mild conditions with simple experimental procedures.
  • Ryo Saito, Michinori Oki
    1982 Volume 55 Issue 8 Pages 2508-2511
    Published: 1982
    Released: June 27, 2006
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    Rotational barriers in 9-[2-(substituted methyl)-1-naphthyl]fluorenes are found not significantly affected by the substituent on the methyl group, ΔG\ eweq’s being ca. 29 kcal/mol at 373 K. Populations of sp- and ap-rotamers at equilibriums show that the sp form is favored to some extent and the results are attributed to entropy factor. OH···π interaction is detected in the ap form of 9-(2-hydroxymethyl-1-naphthyl)fluorene.
  • Masahiro Aoki, Mikio Nakamura, Michinori Oki
    1982 Volume 55 Issue 8 Pages 2512-2515
    Published: 1982
    Released: June 27, 2006
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    9-(2-Methoxy-4,6-dimethylphenyl)fluorenes carrying one or two bromo groups on the phenyl ring were prepared and the buttressing effect on the rotational barrier about the C9–Cph bond were investigated. The free energies of activation for rotation were 26.5, 25.9, and 27.2 kcal/mol at 56 °C for 3-bromo, 5-bromo, and 3,5-dibromo compounds, respectively. The buttressing effect was enhanced when the bromo group was next to the methoxyl group relative to that given to the methyl group. The results were attributed to the fact that a methoxyl group, which gives its steric effect by the oxygen atom in the normal cases, has to take conformations, not coplanar with the phenyl ring, caused by the presence of the bromo group.
  • Tsuneo Fujii, Shigeru Komatsu, Satoshi Suzuki
    1982 Volume 55 Issue 8 Pages 2516-2520
    Published: 1982
    Released: June 27, 2006
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    The fluorescence spectra of biphenyl in an isopentane and methylcyclohexane mixture, in propylene glycol, and in glycerol have been observed as a function of temperature and excitation wavelength. The temperature dependence of the fluorescence spectra is interpreted in terms of the intramolecular geometric relaxation. The fluorescence spectra of biphenyl have been observed in various solvents at room temperature. The Ham effect was found in the biphenyl fluorescence.
  • Isao Kanesaka, Yoshihiro Hiroya, Kiyoyasu Kawai
    1982 Volume 55 Issue 8 Pages 2521-2524
    Published: 1982
    Released: June 27, 2006
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    The method of solving the Laplace equation for a system with axial symmetry is formulated in terms of the finite element method. The molecule having C3V point symmetry is assumed to have axial symmetry, and the van der Waals radii of the component atoms are used to estimate the shape of the central molecule. The method is applied to the IR intensity of the C≡N stretching mode of acetonitrile in various states. The observed intensities are adequately explained by the use of the local and reaction fields, except for the intensity in a solution diluted infinitely in chloroform. The intensity in chloroform can, however, reasonably be explained by taking the hydrogen bond into consideration.
  • Hiroshi Awano, Katsumichi Ono, Kenkichi Murakami
    1982 Volume 55 Issue 8 Pages 2525-2529
    Published: 1982
    Released: June 27, 2006
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    A method for the analysis of ion binding to a neutral polymer, such as poly(oxyethylene) (POE), based on the one-dimensional lattice model has been proposed. The grand partition function for the one-dimensional lattice has been given by the product of the statistical weight matrix. Interaction between the ions bound to the lattice points has been well approximated by the Debye-Hückel pair-by-pair potential, and the distance between the bound ions has been assumed to be the root mean square end-to-end distance of the partial chain. Based on the model, an equilibrium constant has been defined which is referred to the binding constant.
  • Hiroshi Awano, Katsumichi Ono, Kenkichi Murakami
    1982 Volume 55 Issue 8 Pages 2530-2536
    Published: 1982
    Released: June 27, 2006
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    The conductivities for several solutions of alkali metal salts, such as potassium thiocyanate, containing poly(oxyethylene) (POE) have been measured as functions of the POE concentration, Cp. A decrease in the conductivity with an increase in Cp has been observed, particularly in methanol, acetonitrile, propylene carbonate, and sulfolane. For these systems, the binding of the cation has been evaluated from the decrease in conductivity and analyzed by a method based on the one-dimensional lattice model. As well as the solvent effects, the effects of the salt concentration and the effect of the alteration of salt on the binding constant have been discussed.
  • Kozo Inuzuka, Akira Fujimoto
    1982 Volume 55 Issue 8 Pages 2537-2540
    Published: 1982
    Released: June 27, 2006
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    When the dimer-formation energy of 2-pyridone was measured by means of 1H-NMR spectroscopy, the value of 65.3 kJ mol−1 was obtained. It is much larger than the hydrogen-bond energies which are generally observed for the C=O···H–N system. The dimer-formation energy of 2-pyridone was calculated by means of the CNDO/2 method; its formation energy (−ΔH) was estimated to be 68.2 kJ mol−1. The electronic structures of the monomer and dimer of 2-pyridone were calculated by means of the CNDO method with configuration interaction (CNDO/CI) in order to clarify the previous band assignment of the UV spectrum of 2-pyridone. According to the calculated results, the absorption bands at 305 and 228 nm in isooctane (2,2,4-trimethylpentane) were assigned to the monomer, while those at 297.5 and 230.5 nm were assigned to the dimer.
  • Tetsuo Katsuyama, Toshihiko Kumai
    1982 Volume 55 Issue 8 Pages 2541-2546
    Published: 1982
    Released: June 27, 2006
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    The ligand-substitution reactions between two multidentate ligand complexes in the presence of free ligands proceed by means of a coordination chain-reaction mechanism. The reaction was simulated on a computer under various conditions. The character of the steady state of the free ligands in the coordination chain reaction was discussed. The conditions under which the coordination chain reaction proceeds with the steady state of the free ligands were determined. The diagrams of the time development of the free ligands were found to be useful for studies using the coordination chain reaction.
  • Kunio Takeda
    1982 Volume 55 Issue 8 Pages 2547-2550
    Published: 1982
    Released: June 27, 2006
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    A single relaxation was found in the system of sodium dodecyl sulfate and bovine serum albumin using a pressure-jump method with conductivity detection. The relaxation was observed in the concentration range of the surfactant below the critical micelle concentration. The relaxation time becomes fast with the stepwise formation of a complex between them and finally attains values compatible with those in the system of the pure surfactant micelle. This suggests a correlation of the relaxation phenomena with the partial breakdown and reformation of the complex. The similarity of the complex to the surfactant micelle was discussed on the basis of the kinetic aspects of the interaction of the surfactant with the protein.
  • Kinya Iijima, Eiichi Koshimizu, Shuzo Shibata
    1982 Volume 55 Issue 8 Pages 2551-2554
    Published: 1982
    Released: June 27, 2006
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    The molecular structure of trimethylphosphine-boron triiodide (CH3)3P·BI3 has been determined by means of gas-electron diffraction. The molecular parameters and their uncertainties were rg(B–I)=2.233±0.003 Å, rg(P–B)=1.947±0.011 Å, rg(C–P)=1.809±0.003 Å, rg(C–H)=1.094±0.008 Å, ∠IBI=111.6±0.3°, and ∠CPC=106.0±0.5°. The gaseous molecule was rigid with respect to the rotational vibration around the P–B bond.
  • Toshihide Baba, Junya Sakai, Hideki Watanabe, Yoshio Ono
    1982 Volume 55 Issue 8 Pages 2555-2559
    Published: 1982
    Released: June 27, 2006
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    Dodecatungstophosphoric acid (TPA) is a very effective catalyst for the conversion of methanol into hydrocarbons. The effects of the reaction parameters, such as the temperature or the methanol partial pressure, were therefore examined. The kinetic features of the conversion over TPA are quite different from those over ZSM-5 zeolites. This difference is caused by the unique nature of the conversion over TPA; methanol molecules are sorbed and undergo the conversion in the bulk of solid TPA.
  • Yoshimi Kurimura, Kimiyo Katsumata
    1982 Volume 55 Issue 8 Pages 2560-2563
    Published: 1982
    Released: June 27, 2006
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    The visible-light-induced reduction of methyl viologen was found to occur in water-swollen cation-exchange resin, which adsorbed both Ru(bpy)32+ and methyl viologen (RMCA resin) with the aid of triethanolamine (TEA) as a donor. With illumination, the generation of hydrogen peroxide proceeds in an oxygenated TEA solution containing RMCA resin. Hydrogen peroxide is produced via the superoxide ion, which is itself formed by the reaction of the methyl viologen radical in the resin with the oxygen molecule in the bulk of the solution. The Ru(bpy)32+-photosensitized reaction processes leading to the generation of methyl viologen radical and hydrogen peroxide in the heterogeneous systems are discussed on the basis of the results obtained.
  • Takeshi Watanabe, Hiroko Shimada, Ryoichi Shimada
    1982 Volume 55 Issue 8 Pages 2564-2571
    Published: 1982
    Released: June 27, 2006
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    The infrared and Raman spectra of 2-methylpyrazine were studied. An assignment was given for all fundamental vibrations based on the polarization behavior of the spectral bands and on the normal coordinate analysis. The magnetic effect on the phosphorescence lifetime and the time-resolved and polarized phosphorescence spectra of this molecule were investigated at 1.4 K. From the analysis of the phosphorescence, (1) the short lifetime phosphorescence was assigned to the emission arising from the most emissive y″ sublevel, as in the case of pyrazine, (2) the long lifetime phosphorescence was assigned to the emissions arising from the x and z″ sublevels, whose lifetimes were roughly equal to each other and (3) the 0-0 and totally symmetric vibronic bands, and the out-of-plane vibronic bands observed in the long lifetime phosphorescence, were ascribed to the z″ and x sublevel emissions, respectively.
  • Kazuo Tsutsumi, Seiichi Hagiwara, Yoshio Mitani, Horoshi Takahashi
    1982 Volume 55 Issue 8 Pages 2572-2575
    Published: 1982
    Released: June 27, 2006
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    A high-temperature calorimeter of the twin conduction type was designed with the capability of measuring heats of adsorption of gases on solids in the temperature range RT to 700 K. A chromel-alumel thermopile was used as the detector and a volumetric adsorption apparatus was equipped. Its calibration and preliminary experiments on heats of adsorption of ammonia on zeolites are described.
  • Kazuko Katsuki, Kyunosuke Majima
    1982 Volume 55 Issue 8 Pages 2576-2580
    Published: 1982
    Released: June 27, 2006
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    Sodium-calcium zeolite minerals were synthesized in an electric oven at 80 °C for 1–5 weeks from suspensions of a suitable combination of the starting materials, which had a chemical composition of 2nNa2O·2CaO·Al2O3·nSiO2·xH2O(4≤n≤20, x=83–610). All of the synthetic products were obtained as massive products in the gel. X-Ray and IR analyses and a quantitative analysis of the principal ingredients showed these massive products to be well-crystallized hydroxycancrinites which contained 0–4.9% calcium oxide.
  • Takayuki Matsushita, Hiroshi Kono, Mitsuru Nishino, Toshiyuki Shono
    1982 Volume 55 Issue 8 Pages 2581-2587
    Published: 1982
    Released: June 27, 2006
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    A series of monomeric chloroiron(III) complexes with the quadridentate or quinquedentate Schiff bases such as N,N′-disalicylideneethylenediamine or bis[3-(salicylideneamino)propyl]amine react with superoxide ions, O2, in dimethyl sulfoxide to give the corresponding μ-oxo dimers. The polymeric chloroiron(III) complexes with the polymeric (oligomeric) Schiff bases derived from 5,5′-methylenedisalicylaldehyde and triamines react with O2 in dimethyl sulfoxide to give the oxygenated complexes, probably dioxygen adducts, FeIII–O2. This is suggested by the absorption spectra and the polarographic measurements.
  • Nobuko Hatanaka
    1982 Volume 55 Issue 8 Pages 2588-2593
    Published: 1982
    Released: June 27, 2006
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    The peak height of the square-wave (s.w.) polarogram of lead increased markedly upon the addition of anions forming insoluble compounds with lead, and the temperature coefficient of the peak height showed a negative value, different from the theoretical value in a diffusion-controlled or an electrode-reaction-rate-controlled process at the following concentrations of anions; [Cl]=1 M, [Br]=10−2 M, [SCN]=10−1 M for 10−4 M lead. In the case of the addition of iodide, the s.w. peak height of lead increased at concentrations of iodide above 10−4 M for 10−4 M lead but the temperature coefficient of the peak height was always positive. Moreover, another peak due to lead appeared superimposed on the oxidation peak of iodide at a more positive potential, and this peak had a negative temperature coefficient. It was found that these phenomena were attributable to a specific adsorption of lead on mercury electrodes, induced by the foremost adsorbed anions. However in the case of the addition of iodide or in that of a high concentration of bromide or thiocyanate, the reversibility of the electrode process decreased and the temperature coefficient varied to a positive value in spite of the increase in adsorbed depolarizers.
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