- Medium effects on the direct cis-trans photoisomerization of 1,4-diphenyl-1,3-butadiene in solution
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Quantum yields for the photoisomerization of trans,trans-1,4-diphenyl-1,3- butadiene (tt-DPB), determined in benzene, cyclohexane, methylcyclohexane, hexane, and perfluorohexane, confirm the low values reported earlier for benzene and cyclohexane and reveal even lower values in the last two solvents. In contrast to trans-stilbene (t-St), fluorescence and torsional relaxation leading to photoisomerization do not account exclusively for S1tt-DPB decay. Competing radiationless singlet excited-state decay pathways exist in tt-DPB, which do not lead to photoisomerization and may not involve large-amplitude torsional motions. Our results invalidate analyses of tt-DPB fluorescence quantum yields and lifetimes that assign all radiationless decay to the isomerization channel. Gas-phase chromatography analysis of tt-DPB photoisomerization in hexane shows the reaction to be concentration-independent and reveals, for the first time, a significant, two-bond photoisomerization pathway, βtt→tc = 0.092 and βtt→cc = 0.020. The dominant one-bond-twist (OBT) process is accompanied by a bicycle pedal (BP) process that accounts for almost 20% of tt-DPB photoisomerization. The OBT tt-DPB photoisomerization quantum yield is largest in benzene (Bz) and smallest in perfluorohexane (PFH). Contrary to expectations, reduction in medium friction in PFH is accompanied by a decrease in βtt→tc. The 11Bu/21Ag order and energy gap appear to control the contribution of torsional relaxation to radiationless decay. Lowering the 11Bu energy as in Bz favors photoisomerization. Reversal of the 11Bu/2 1Ag order in PFH is accompanied by short τf and small βf and βtt→tc values that suggest the presence of competing 21Ag → 1 1Ag relaxation paths that are unproductive with respect to photoisomerization. We conclude that the Birks extension to diphenylpolyenes of the Orlandi-Siebrand cis-trans photoisomerization mechanism is not valid. Photoisomerization appears to occur in the 1IBu state, and we argue that this applies to t-St as well.
- Saltiel, Jack,Krishna, Talapragada R. S.,Laohhasurayotin, Kritapas,Ren, Yanjun,Phipps, Kathleen,Davis, Paul H.,Yee, W. Atom
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Read Online
- Cobalt-Catalyzed Z to e Geometrical Isomerization of 1,3-Dienes
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An efficient cobalt-catalyzed geometrical isomerization of 1,3-dienes is described. In the combination of a CoCl2 precatalyst with an amido-diphosphine-oxazoline ligand, the geometrical isomerization of E/Z mixtures of 1,3-dienes proceed in a stereoconvergent manner, affording (E) isomers in high stereoselectivity. This facile transformation features a broad substrate scope with good functional group tolerance and could be scaled up to the gram scale smoothly with a catalyst loading of 1 mol %.
- Wang, Wei,He, Shuying,Zhong, Yuqing,Chen, Jianhui,Cai, Cheng,Luo, Yanshu,Xia, Yuanzhi
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- Acetylene as a Dicarbene Equivalent for Gold(I) Catalysis: Total Synthesis of Waitziacuminone in One Step
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The gold(I)-catalyzed reaction of acetylene gas with alkenes leads to (Z,Z)-1,4-disubstituted 1,3-butadienes and biscyclopropanes depending on the donor ligand on gold(I). Acetylene was generated in situ from calcium carbide and water in a user-friendly p
- Armengol-Relats, Helena,Echavarren, Antonio M.,Escofet, Imma,Korber, J. Nepomuk,Scharnagel, Dagmar,de Orbe, M. Elena
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supporting information
p. 4888 - 4891
(2020/02/11)
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- Efficient Z-Selective Semihydrogenation of Internal Alkynes Catalyzed by Cationic Iron(II) Hydride Complexes
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The bench-stable cationic bis(σ-B-H) aminoborane complex [Fe(PNPNMe-iPr)(H)(η2-H2B = NMe2)]+ (2) efficiently catalyzes the semihydrogenation of internal alkynes, 1,3-diynes and 1,3-enynes. Moreover, selective incorporation of deuterium was achieved in the case of 1,3-diynes and 1,3-enynes. The catalytic reaction takes place under mild conditions (25 °C, 4-5 bar H2 or D2) in 1 h, and alkenes were obtained with high Z-selectivity for a broad scope of substrates. Mechanistic insight into the catalytic reaction, explaining also the stereo- and chemoselectivity, is provided by means of DFT calculations. Intermediates featuring a bisdihydrogen moiety [Fe(PNPNMe-iPr)(η2-H2)2]+ are found to play a key role. Experimental support for such species was unequivocally provided by the fact that [Fe(PNPNMe-iPr)(H)(η2-H2)2]+ (3) exhibited the same catalytic activity as 2. The novel cationic bisdihydrogen complex 3 was obtained by protonolysis of [Fe(PNPNMe-iPr)(H)(η2-AlH4)]2 (1) with an excess of nonafluoro-tert-butyl alcohol.
- Gorgas, Nikolaus,Brünig, Julian,St?ger, Berthold,Vanicek, Stefan,Tilset, Mats,Veiros, Luis F.,Kirchner, Karl
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supporting information
p. 17452 - 17458
(2019/11/03)
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- Carbon-carbon bond forming reactions via Pd-catalyzed detellurative homocoupling of diorganyl tellurides
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A simple and highly efficient method for the constructions of Csp-Csp, Csp2-Csp2 and Csp3-Csp3 bonds is reported. The symmetrical diaryl tellurides undergo detellurative homocouplings to afford symmetrical biaryl products. The reactions are carried out at ambient temperature using PdCl2 as a catalyst in the presence of Ag2O and Na2CO3. Similarly, the detellurative homocouplings of dibenzyl telluride and bis(phenylethynyl)telluride give bibenzyl and the conjugated diyne, respectively.
- Zhang, Shaozhong,Kolluru, Lalitha,Vedula, Souseelya K.,Whippie, Drew,Jin, Jin
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supporting information
p. 3594 - 3597
(2017/08/23)
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- Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture
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The intermolecular gold(I)-catalyzed reaction between arylalkynes and alkenes leads to cyclobutenes by a [2 + 2] cycloaddition, which takes place stepwise, first by formation of cyclopropyl gold(I) carbenes, followed by a ring expansion. However, 1,3-butadienes are also formed in the case of ortho-substituted arylalkynes by a metathesis-type process. The corresponding reaction of alkenes with aryl-1,3-butadiynes, ethynylogous to arylalkynes, leads exclusively to cyclobutenes. A comprehensive mechanism for the gold(I)-catalyzed reaction of alkynes with alkenes is proposed on the basis of density functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes.
- De Orbe, M. Elena,Amenós, Laura,Kirillova, Mariia S.,Wang, Yahui,López-Carrillo, Verónica,Maseras, Feliu,Echavarren, Antonio M.
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supporting information
p. 10302 - 10311
(2017/08/09)
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- Unsupported Nanoporous Gold Catalyst for Chemoselective Hydrogenation Reactions under Low Pressure: Effect of Residual Silver on the Reaction
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For the first time, H-H dissociation on an unsupported nanoporous gold (AuNPore) surface is reported for chemoselective hydrogenation of C=C, C=C, C=N, and C=O bonds under mild conditions (8 atm H2 pressure, 90 °C). Silver doping in AuNPore, which was inevitable for its preparation through a process of dealloying of Au-Ag alloy, exhibited a remarkable difference in catalytic activity between two catalysts, Au>99Ag1NPore and Au90Ag10NPore.The former was more active and the latter less active in H2 hydrogenation, while the reverse tendency was observed for O2 oxidation. This marked contrast between H2 reduction and O2 oxidation is discussed. Further, Au>99Ag1NPore showed a high chemoselectivity toward reduction of terminal alkynes in the presence of internal alkynes which was not achieved using supported gold nanoparticle catalysts and other previously known methods. Reductive amination, which has great significance in synthesis of amines due to its atom-economical nature, was also realized using Au>99Ag1NPore, and the Au>99Ag1NPore/H2 system showed a preference for the reduction of aldehydes in the presence of imines. In addition to this high chemoselectivity, easy recovery and high reusability of AuNPore make it a promising heterogeneous catalyst for hydrogenation reactions.
- Takale, Balaram S.,Feng, Xiujuan,Lu, Ye,Bao, Ming,Jin, Tienan,Minato, Taketoshi,Yamamoto, Yoshinori
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supporting information
p. 10356 - 10364
(2016/08/31)
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- Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides
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An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2′-bipyridine) that is both air- and moisture-stable over a period of months was introduced.
- Johnson, Keywan A.,Biswas, Soumik,Weix, Daniel J.
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supporting information
p. 7399 - 7402
(2016/05/24)
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- Quinonediimine-induced oxidative coupling of organomagnesium reagents
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N,N′-Diphenyl-p-benzoquinonediimine, a redox-active unit of polyaniline, efficiently induced the oxidative homocoupling of various aryl- and vinylmagnesium reagents in suppressing the side reactions, such as 1,2- or 1,4-addition reaction. Copyright
- Amaya, Toru,Suzuki, Riyo,Hirao, Toshikazu
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p. 653 - 656
(2014/01/23)
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- Regio- and stereoselective hydrosilylation of 1,3-enynes catalyzed by palladium
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In the presence of Pd(0) and a phosphine, hydrosilylation of 1,3-enynes with Me2SiHCl proceeds to yield dienylsilanes with the silicon function added to the internal alkyne carbon atom and with (E)-configuration of newly formed olefinic bond. The silanols isolated after hydrolysis of the primarily obtained products serve as precursors to conjugated dienes with different substitution patterns.
- Zhou, Hui,Moberg, Christina
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supporting information
p. 1444 - 1447
(2013/06/27)
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- Diastereoselective liquid assisted grinding: 'Cracking' functional resins to advance chromatography-free synthesis
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As regulations that restrict the use of organic solvents become more stringent, ball milling remains an attractive substitute for traditional organic synthesis. However, the mechanochemistry community does not have a purification pathway to complement the solvent-free, ball milling process. Functional resins have proven to be powerful synthetic tools that simplify purification, but traditional handling of these resins restricts their utility, as hazardous organic solvents are needed to swell the resin. Ball milling the functional resin exposes the functional groups as a function of surface area. This report details the use of ball milling and functional resins to perform an environmentally attractive version of the Wittig reaction.
- Shearouse, William C.,MacK, James
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p. 2771 - 2775,5
(2020/09/14)
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- Stereoselective synthesis of disubstituted butadienes via copper-mediated coupling of alkenyl silanes
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A strategy is described for the stereoselective synthesis of substituted (E)-, (Z)-, and -disubstituted butadienes from terminal alkynes by the copper-mediated coupling of geometrically-defined alkenyl silanes. Proof-of-concept results that demonstrate the feasibility of this approach are presented. Georg Thieme Verlag Stuttgart · New York.
- Blackwell, David T.,Galloway, Warren R. J. D.,Spring, David R.
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p. 2140 - 2144
(2011/11/06)
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- Cyclopropanation with gold(I) carbenes by retro-Buchner reaction from cycloheptatrienes
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Cationic gold(I) promotes the retro-Buchner reaction of 7-substituted 1,3,5-cycloheptatrienes, leading to gold(I) carbenes that cyclopropanate alkenes.
- Solorio-Alvarado, César R.,Wang, Yahui,Echavarren, Antonio M.
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supporting information; experimental part
p. 11952 - 11955
(2011/10/04)
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- Synthesis of stilbenes promoted by the mixture of zinc and iron powder
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Stilbenes have been synthesised by a one-pot reaction of aldehydes with benzyl bromide. The reaction was promoted by both triphenylphosphine and the mixture of zinc and iron together in sealed tube. The yields ranged from moderate to excellent.
- Zhanga, Zhiying,Xieb, Yuanyuan,Yua, Xiaochun
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experimental part
p. 140 - 142
(2009/10/15)
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- The reaction of dialkoxytitanacyclopropanes and dialkoxytitanacyclopropenes with carbon dioxide
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Dialkoxytitanacyclopropanes and dialkoxytitanacyclopropenes react with one molecule of carbon dioxide to afford diversely substituted carboxylic acids after hydrolysis.
- Six, Yvan
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p. 1159 - 1160
(2007/10/03)
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- Selective liquid-phase semihydrogenation of functionalized acetylenes and propargylic alcohols with silica-supported bimetallic palladium-copper catalysts
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Silica-supported, bimetallic palladium-copper catalysts were prepared in solution under mild conditions by reacting lithium di(4-tolyl)cuprate with palladium acetate in the presence of silica particles. Small bimetallic palladium-copper particles were deposited on the silica surface as confirmed with TEM-EDAX and EXAFS. The new material has been applied as catalyst in the liquid-phase semihydrogenation of mono- and disubstituted alkynes and showed high selectivity toward the cis-alkenes. The influence of addition of quinoline or potassium hydroxide to the semihydrogenation reaction mixture and the effects of exposure of the catalyst to air before use have been investigated. Silica-supported, bimetallic palladium-copper catalysts were prepared in solution under mild conditions by reacting lithium di(4-tolyl)cuprate with palladium acetate in the presence of silica particles. Small bimetallic palladium-copper particles were deposited on the silica surface as confirmed with TEM-EDAX and EXAFS. The new material has been applied as catalyst in the liquid-phase semihydrogenation of mono- and disubstituted alkynes and showed high selectivity toward the cis-alkenes. The influence of addition of quinoline or potassium hydroxide to the semihydrogenation reaction mixture and the effects of exposure of the catalyst to air before use have been investigated.
- Spee,Boersma,Meijer,Slagt,Van Koten,Geus
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p. 1647 - 1656
(2007/10/03)
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- Nickel-catalyzed electrochemical couplings of vinyl halides: Synthetic and stereochemical aspects
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Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, β,γ- or γ,δunsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene.
- Cannes,Condon,Durandetti,Perichon,Nedelec
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p. 4575 - 4583
(2007/10/03)
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- Palladium-catalyzed homocoupling reactions of organic tellurides
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Organic tellurides containing a styryl moiety react in acetonitrile to give the corresponding homocoupling products, 1,3-dienes, with moderate to quantitative yields in the presence of a catalytic amount of Pd(OAc)2 together with AgOAc at 25 °C. In contrast, such homocoupling reactions hardly occur with diaryl, alkyl aryl, dialkyl, and alkynyl aryl tellurides, even at reflux temperature and in the presence of a stoichiometric amount of palladium salt, in disagreement with reported results. The result of cross-over experiments suggests that this homocoupling reaction occurs between an alkenyl telluride and an alkenylpalladium species, the latter being formed via the migration of an alkenyl moiety from Te to Pd (transmetallation).
- Nishibayashi, Yoshiaki,Cho, Chan Sik,Ohe, Kouichi,Uemura, Sakae
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p. 335 - 339
(2007/10/03)
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- Electron transfer induced isomerization of cis,trans- and trans,trans-1,4-diphenyl-1,3-butadiene
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Irradiation of cis,trans- or trans,trans-1,4-diphenyl-1,3-butadiene with 9,10-dicyanoanthracene as a sensitizer results in predominant cis,trans → trans,trans geometric isomerization in acetonitrile. A cation radical chain mechanism is proposed to be oper
- Wakamatsu, Kan,Takahashi, Yasutake,Kikuchi, Koichi,Miyashi, Tsutomu
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p. 5681 - 5684
(2007/10/02)
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- Ni(0)-Triphenylphosphine Complex-Catalyzed Homo-Coupling of 1-Alkenyl Halides with Zinc Powder
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The homo-coupling of 1-alkenyl halides was examined in the presence of NiBr2(PPh3)2, PPh3, and excess zinc.The reactions proceed under very mild conditions to give high yields of conjugated dienes.The addition of KI or thiourea was unnecessary for a successful reaction, in contrast with systems without an external phosphine ligand.
- Sasaki, Ken,Nakao, Kikuji,Kobayashi, Yoshihiko,Sakai, Mutsuji,Uchino, Norito,et al.
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p. 2446 - 2448
(2007/10/02)
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- Styryl coupling vs. styryl acetate formation in reactions of styryl tellurides with palladium(II) salts
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In sharp contrast to the expected formation of a telluride-palladium complex, the treatment of either (E,E)- and (Z,Z)-distyryl tellurides (1 and 2) or (E)- and (Z)-styryl phenyl tellurides (5 and 6) with Li2PdCl4 in acetonitrile at 25 deg C results in the formation of stereoisomeric 1,4-diphenylbuta-1,3-dienes, whereas the treatment of 1 and 2 with Pd(OAc)2 produces styryl acetates solely or mainly.
- Uemura, Sakae,Takahashi, Hidetaka,Ohe, Kouichi
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- Pulse Radiolysis Study of Ion Pairing of Diphenylpolyene Radical Anions with Tetrabutylammonium and Sodium Cations in Tetrahydrofuran
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Pulse radiolysis of tetrahydrofuran (THF) solutions of all-trans α,ω-diphenyl-substituted polyenes, such as 1,4-diphenylbuta-1,3-diene, 1,6-diphenylhexa-1,3,5-triene and 1,8-diphenylocta-1,3,5,7-tetraene, has been undertaken in the absence and presence of Bu4NPF6 and NaBPh4.In the presence of the salts, the absorption maxima of the diphenylpolyene radical anions are shifted to shorter wavelengths by ion pairing with Bu4N+ and Na+ as well as that of the trans-stilbene radical anion previously investigated.When Ph(CH=CH)nPH.- (n=1-4) is paired with Bu4N+, the magnitude of the spectroscopic shift is larger for n=2-4 than for n=1.On the other hand, the magnitude of the spectroscopic shift due to the ion pairing with Na+ decreases with increasing n and becomes very small in the case of n=3 or 4.The decay of the radical anions, which is due to neutralization reactions with THF(H+), is retarded by the addition of the salts.The retarding effect of the salts is attributed to the ion pairing of the reactant ions with the counterions derived from the salts.In acetonitrile solution the absorption spectra and the decay rates of the radical anions are not affected by the addition of the salts, demonstrating that the ion pairing is not important in such a polar solvent.Results for the radical anions of pyrene, perylene and triphenylethylene are presented for the sake of comparison.The appreciable spectroscopic shift due to the ion pairing with the large Bu4N+ ion was found to be characteristic of the diphenylpolyene radical anions.
- Aoyama, Takahisa,Yamamoto, Yukio,Hayashi, Koichiro
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p. 3353 - 3358
(2007/10/02)
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- A Pulse Radiolysis Study of the Formation of Dimer Radical Cations of Aromatic Olefins
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The formation of dimer radical cations of several aromatic olefins has been studied by the pulse radiolysis technique.The aromatic olefins examined are 2-vinylnaphthalene (VN), 2-(1-propenyl)naphthalene (PN), 4-vinylbiphenyl (VBP), trans,trans-1,4-diphenyl-1,3-butadiene (1,4-DPB), and s-trans-2,3-diphenyl-1,3-butadiene (2,3-DPB).The formation of dimer radical cations were observed with all of them except 1,4-DPB, although it was very limited with VBP.Two types of dimer radical cations, bonded and associated ones, are formed with VN, whereas only the associated dimer radical cation is formed with PN.The influence of the aromatic substituents on the formation of the dimer radical cations is described.
- Chikai, Yukio,Yamamoto, Yukio,Hayashi, Koichiro
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p. 2281 - 2286
(2007/10/02)
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- DITHIOL-FERROUS CHLORIDE CATALYZED SELECTIVE REDUCTION OF ALKYNES WITH SODIUM BOROHYDRIDE
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Simple dithiols-ferrous chloride or lipoamide-ferrous chloride were found to be effective catalysts for the selective reduction of substituted alkynes to alkenes with sodium borohydride presumably by forming active dithiol-Fe(II) complexes.
- Kijima, Masashi,Nambu, Yoko,Endo, Takeshi
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p. 1851 - 1854
(2007/10/02)
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- Stereochemistry of Halogen-Metal Exchange Reaction of Vinyl Halide with Grignard Reagent
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Halogen-magnesium exchange was confirmed to proceed with stereospecific retention of configuration in the reaction of β-bromostyrene and butylmagnesium bromide.
- Sugita, Toshio,Sakabe, Yo-ichi,Sasahara, Toshiaki,Tsukada, Mitsunori,Ichikawa, Katsuhiko
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p. 2319 - 2320
(2007/10/02)
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- ACTIVATION OF REDUCING AGENTS. SODIUM HYDRIDE CONTAINING COMPLEX REDUCING AGENTS XIX. HOMO COUPLING OF ARYL AND VINYL HALIDES PROMOTED BY LIGAND MODIFIED NiCRA (NaH-RONa-Ni(OAc)2)
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The preparation of NiCRA (NaH-t-AmONa-Ni(OAc)2) in the presence of 2,2'-bipyridine (bpy) leads to a new reagent (termed NiCRA-bpy) which is shown to be one of the most efficient Ni based reagents reported so far for the homocoupling of aryl and vinyl halides (including chlorides).The homo coupling of cis- and trans-β-bromostyrenes is shown to be stereospecific.
- Vanderesse, Regis,Brunet, Jean-Jacques,Caubere, Paul
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p. 263 - 272
(2007/10/02)
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- IN SITU-GENERATED NICKEL(0)-CATALYZED HOMO-COUPLING OF ALKENYL HALIDES WITH ZINC POWDER. A SPECIFIC OUTCOME IN STEREOCHEMISTRY.
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The catalytic activity of nickel(0) generated in situ from nickel(II) salt was examined in a dehalogenative coupling of alkenyl halides with zinc powder. The reaction of alkenyl bromides took place provided that potassium iodide was present to assist the reduction of nickel(II) with zinc powder, and also to convert the alkenyl bromides to the corresponding alkenyl iodides. A speculative view concerning the disproportionation step is advanced in an attempt to explain the unique sterochemistry observed.
- Takagi,Mimura,Inokawa
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p. 3517 - 3522
(2007/10/02)
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- A Synthesis of Conjugated Dienes from Aromatic, Five-membered Heterocycles
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Reactions of furan, thiophene, selenophene, and tellurophene as well as 2-methyl and 2,5-dimethyl derivatives of the first two heterocycles with phenyl-, methyl-, and n-butyl-magnesium bromides in the presence of ligated nickel dichloride are shown to yield buta-1,3-dienes mostly with retention of configuration.
- Wenkert, Ernest,Leftin, Michael H.,Michelotti, Enrique L.
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p. 617 - 618
(2007/10/02)
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- NICKEL-CATALYZED ULLMANN-TYPE COUPLING OF ALKENYL HALIDES WITH ZINC POWDER
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Convenient procedure for an Ullmann-type coupling of alkenyl halides using zinc powder, nickel(II) chloride, and potassium iodide and/or thiourea is presented.One double bond in the produced diene retained the configuration of a starting material, while partial cis-trans isomerization was observed in the second one.
- Takagi, Kentaro,Hayama, Naomi
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p. 637 - 638
(2007/10/02)
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- A CONVENIENT METHOD FOR THE CONVERSION OF trans to cis-CINNAMIC ACIDS
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trans-Cinnamic acids react in sequence with bromine, base, and carbon monoxide to give cis-acids in reasonable yields.
- Galamb, Vilmos,Alper, Howard
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p. 2965 - 2968
(2007/10/02)
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