42 research outputs found

    Caracterização mecânica de paredes de alvenaria em construções antigas: ensaios com macacos planos

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    A reabilitação edifícios antigos, construídos com paredes de alvenaria resistentes, exige a caracterização dos materiais constituintes e das soluções construtivas existentes. A falta de conhecimento das construções antigas conduz, por vezes, a intervenções com recurso a técnicas intrusivas, descaracterizando a autenticidade do património construído. Com este trabalho pretende-se apresentar os resultados de uma campanha de ensaios usando macacos planos para o conhecimento do comportamento mecânico das alvenarias antigas, incentivando a preservação, consolidação e reforço destas estruturas com técnicas adequadas. Os ensaios com macacos planos permitem a caracterização da alvenaria: informação acerca do estado de tensão instalado nas paredes, resistência à compressão, módulo de elasticidade, informação fundamental quando se analisa as construções antigas

    Remote Intramolecular Functionalization Of Arylnitrenium Ions. Ipso-substitution And Spiro-lactone Formation

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    Acid-catalysed decomposition of (4′-azidophenyl)propanoic and butyric acids leads to ipso-attack by the carboxy group para to the nitrenium ion and the formation of imines of cyclohexadienone spiro-lactones, which can rearrange to the benz-fused lactones; 4′-azido-2-carboxydiphenyl ether behaves the same way to give spiro-lactone (9).428328

    Efficient α-methylenation Of Carbonyl Compounds In Ionic Liquids At Room Temperature

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    The application of several 1-butyl-3-methylimidazolium (BMIM) salt ionic liquids as solvent in the α-methylenation of carbonyl compounds at room temperature is reported. The ionic liquid [BMIM][NTf 2] gave a clean reaction in a short time and good yields of several α-methylene carbonyl compounds. This ionic liquid was reused without affecting the reaction rates or yields over seven runs. © Georg Thieme Verlag Stuttgart.17578Stiger, K.D., Mar-Tang, R., Bartlet, P.A., (1999) J. Org. Chem, 64, p. 8409Weingarten, M.D., Skudlarek, J., Sikorski, J.A., (2006), PCT Int. Appl. WO 2006004903Mori, K., Yajima, A., Takikawa, H., (1996) Liebigs. Ann, p. 891Picman, A.K., (1986) Biochem. Syst. Ecol, 14, p. 255Schmidt, T.J., (1999) Curr. Org. Chem, 3, p. 577Basavaiah, D., Rao, A.J., Satyanarayana, T., (2003) Chem. Rev, 103, p. 811Kagan, H.B., Riant, O., (1992) Chem. 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Commun, p. 2041Hon, Y.S., Chang, F.-J., Lu, L., Lin, W.C., (1998) Tetrahedron, 54, p. 5233Hon, Y.S., Chen, H.F., (2007) Tetrahedron Lett, 48, p. 8611Hon, Y.S., Hsieh, C.H., (2006) Tetrahedron, 41, p. 9713Hon, Y.S., Hsieh, C.H., Liu, Y.W., (2005) Tetrahedron, 61, p. 2713Hon, Y.S., Liu, Y.W., Hsieh, C.H., (2004) Tetrahedron, 60, p. 4837For the total synthesis of brevetoxin B (second to last step), see: (a) Nicolaou, K. C.Rutjes, F. P. J. T.Theodorakis, E. A.Tiebes, J.Sato, M.Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173Nicolaou, K.C., Reddy, K.R., Skokotas, G., Fuminori, S., Xiao, X.-Y., (1992) J. Am. Chem. Soc, 114, p. 7935. , See also: bCrimmins, M.T., Stanton, M.G., Allwein, S.P., (2002) J. Am. Chem. Soc, 124, p. 5958. , For the total synthesis of laulimalide, see: cAhmed, A., Hoegenauer, E.K., Enev, V.S., Hanbauer, M., Kaehlig, H., Ohler, E., Mulzer, J., (2003) J. Org. 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Chem, 5, p. 671Yadav, J.S., Reddy, B.V.S., Gayathri, K.U., Prasad, A.R., (2003) New J. Chem, 27, p. 1684Hajipour, A.R., Rafiee, F., Ruoho, A.E., (2007) Synlett, p. 1118Akike, J., Yamamoto, Y., Togo, H., (2007) Synlett, p. 2168Lancaster, N.L., Llopis-Mestre, V., (2003) Chem. Commun, p. 2812Mehnert, C.P., Dispenziere, N.C., Cook, R.A., (2002) Chem. Commun, p. 1610Chiappe, C., Piccioli, P., Pieraccini, D., (2006) Green Chem, 8, p. 277Santos, L.S., Neto, B.A.D., Consorti, C.S., Pavam, C.H., Almeida, W.P., Coelho, F., Dupont, J., Eberlin, M.N., (2006) J. Phys. Org. Chem, 19, p. 731Yang, X.-F., Wang, M., Varma, R.S., Li, C.-J., (2003) Org. Lett, 5, p. 657Zhao, G., Jiang, T., Gao, H., Han, B., Huang, J., Sun, D., (2004) Green Chem, 6, p. 75Eckstein, M., Filho, M.V., Liese, A., Kragl, U., (2004) Chem. Commun, p. 1084Lou, W., Zong, M., Smith, T.J., (2006) Green Chem, 8, p. 147Gamba, M., Lapis, A.A.M., Dupont, J., (2008) Adv. Synth. Catal, 350, p. 160Zhang, C.Z., (2006) Adv. Catal, 49, p. 153Jain, N., Kumar, A., Chauban, S., Chauban, S.M.S., (2005) Tetahedron, 61, p. 1015Cassol, C.C., Eberling, G., Ferrera, B., Dupont, J., (2006) Adv. Synth. Catal, 324, p. 243Dupont, J., (2004) J. Braz. Chem. Soc, 15, p. 341Rosa, J.N., Afonso, C.A.M., Santos, A.G., (2001) Tetrahedron, 57, p. 4189Kumar, A., Pawar, S.S., (2003) J. Mol. Catal. A: Chem, 208, p. 33Marsh, K.N., Boxall, J.A., Lichtenthaler, R., (2004) Fluid Phase Equilibria, 219, p. 93Jiang, Y.-Y., Wang, G.-N., Zhou, Z., Wu, Y.-T., Geng, J., Zhang, Z.-B., (2008) Chem. Commun, p. 505Pihko, P.M., Erkkila, A., (2006) J. Org. Chem, 71, p. 2538Spectroscopic Data for Ethyl 3-Methylene-2-oxo-4-phenylbutanoate (1) 1H NMR (300 MHz, CDCl3, δ, 1.36 (t, 3 H, J, 9 Hz, 3.65 (s, 2 H, 4.35 (q, 2 H, J, 9 Hz, 5.98 (s, 1 H, 6.23 (s, 1 H, 7.25 (m, 5 H, 13C NMR (75.5 MHz, CDCl3, δ, 14.0, 35.7, 62.2, 126.5, 128.6, 129.2, 133.1, 137.6, 144.4, 163.9, 188.1. MS: m/z, 218 (5, M, 189 (4, 145 (43, 117 (100, 115 (76, 91 (40, 65 (18, 51 (19, Spectroscopic Data for Ethyl 2-Methylene-3-oxo-3-phenylpropionate(2) 1H NMR (300 MHz, CDCl3, δ, 1.10 (t, 3 H, J, 7.1 Hz, 4.19 (q, 2 H, J, 7.2 Hz, 6.2 (s, 1 H, 6.65 (s, 1 H, 7.44 (d, 2 H, J, 7.2 Hz, 7.52 (t, 1 H, J, 7.3 Hz, 7.84 (d, 2 H, J, 7.2 Hz, 13C NMR (75.5 MHz, CDCl3, δ, 14.0, 61.5, 128.5, 129.4, 131.3, 133.5, 136.3, 141.5, 164.0, 193.0. MS: m/z, 204 11, MYamauchi, M., Katayama, S., Watanabe, T., (1982) Synthesis, p. 935Hon, Y.-S., Hsu, T.-R., Chen, C.-Y., Lin, Y.-H., Chang, F.-J., Hsieh, C.-H., Szu, P.-H., (2003) Tetrahedron, 59, p. 1509Chatani, N., Kamitani, A., Oshita, M., Fukumoto, Y., Murai, S., (2001) J. Am. Chem. Soc, 123, p. 1268

    Strong Hydrogen Bonds In Dicarboxylics Acids And Aromatics Diamines [ligações Hidrogênio Fortes Em ácidos Dicarboxílicos E Diaminas Aromáticas]

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    A very short-strong hydrogen bond (<2 Å, >20kcal/mol) is found in the monoanion of certain dicarboxylic acids derived from maleic and dialkylmalonic acids. Certain aromatic diamines that are known as proton sponge have exceptionally high basicity (pKa) and are only monoprotonated with strong acids like percloric acid. The closed proximity between the two basic centers provokes a strong steric interaction that is relieved upon protonation. Similar effects are found in dicarboxylic acids (hydrogen maleate and hydrogen dialkylmalonates) that present a very short distance between the two oxygens and a short-strong hydrogen bond.236812817Hibbert, F., Emsley, J., (1990) Adv. Phys. Org. Chem., 26, p. 255Jeffrey, G.A., (1997) An Introduction to Hydrogen Bond, , Oxford Univ. Press, New YorkGilli, P., Bertolasi, V., Ferreti, V., Gilli, G., (1994) J. Am. Chem. Soc., 116, p. 909Schwartz, B., Drueckhammer, D.G., (1995) J. Am. Chem. Soc., 117, p. 11902Kato, Y., Toledo, L.M., Rebek Jr., J., (1996) J. Am. Chem. Soc., 118, p. 8575Warshel, A., Papazyan, A., (1996) Proc. Natl. Acad. Sci. U.S.A., 93, p. 13665Kumar, G.A., McAllister, M.A., (1998) J. Am. Chem. Soc., 120, p. 3159Schiott, B., Iversen, B.B., Madsen, G.K.H., Bruice, T.C., (1998) J. Am. Chem. Soc., 120, p. 12117Garcia-Viloca, M., González-Lafont, A., Lluch, J., (1997) J. Am. Chem. Soc., 119, p. 1081Garcia-Viloca, M., Gelabert, R., González-Lafont, A., Moreno, M., Lluch, J.M., (1998) J. Am. Chem. Soc., 120, p. 10203Currie, M., Speakman, J.C., (1970) J. Chem. Soc. A, p. 19230Küppers, H., Kvick, A., Olovsson, J., (1981) Acta Crystallogr., B37, p. 1203Hadzi, D., (1998) J. Mol. Struct., 432, p. 257Perrin, C.L., (1994) Science, 266, p. 1665Perrin, C.L., Kim, Y.J., (1998) J. Am. Chem. Soc., 120, p. 12641Perrin, C.L., Nielson, J.B., Kim, Y.J., (1998) Ber. Bunsenges. Phys. Chem., 102, p. 403Gopalan, R.S., Kumaradhas, P., Kulkarni, G.U., Rao, C.N.R., (2000) J. Mol. Struct., 521, p. 91Garcia-Viloca, M., González-Lafont, À., Lluch, J.M., (1999) J. Am. Chem. Soc., 121, p. 9198Frey, P.A., Whitt, S.A., Tobin, J.B., (1994) Science, 264, p. 1927Gunnarson, G., Wennerstön, H., Egan, W., Forsén, S., (1976) Chem. Phys. Lett., 38, p. 96Bruck, A., McCoy, L.L., Kilway, K.V., (2000) Org. Lett., 2, p. 2007Murthy, A.J.N., Bhat, S.N., Rao, C.N.R., (1970) J. Chem. Soc. A, p. 1251McAllister, M.A., (1997) Can. J. Chem., 75, p. 1195Marimanikkuppam, S.S., In-Sook, H.L., Binder, D.A., Young, V.G., Kreevoy, M.M., (1996) Croat. Chem. Acta, 69, p. 1661Jenks, W.P., Regenstein, J., (1975) Handbook of Biochemistry and Molecular Biology, 1, p. 305. , H. A. Sober, Ed., Chem Ruub. Co., Cleveland, 3rd edMcDonagh, A.F., Phimister, A., Boidjiev, S.E., Lightner, D.A., (1999) Tetrahedron Lett., 40, p. 8515McAllister, M.A., (1997) Can. J. Chem., 75, p. 1195Frey, P.A., Whitt, S.A., Tobin, J.B., (1994) Science, 264, p. 1927Zhao, Q., Abeygunawardana, C., Talalay, P., Mildvan, A., (1996) Proc. Natl. Acad. Sci. USA, 93, p. 8220Ash, E.L., Sudmeier, J.L., DeFabo, E.C., Bachovchin, W.W., (1997) Science, 278, p. 1128Utilizamos o método AMI presente no programa HyperChem R3, Versão 3.0, , da AutoDesk, IncDewar, M.J.S., Zoebisch, E.G., Healy, E.F., Stewart, J.J., (1985) J. Am. Chem. Soc., 107, p. 3902Proton-Sponge é um termo criado pela Aldrich Chemicals Co., Milwaukee - USA, como um nome comercialAlder, R.W., Bowman, P.S., Steele, W.R.S., Winterman, D.R., (1968) J. Chem. Soc., Chem. Commun., p. 723Alder, R.W., Goode, N.C., Miller, N., Hibbert, F., Hunte, K.P.P., (1978) J. Chem. Soc., Chem Commun., p. 89Alder, R.W., Bryce, M.R., Goode, M.R., (1982) J. Chem. Soc., Perkin Trans 2, p. 477Hibbert, F., (1974) J. Chem. Soc., Perkin Trans 2, p. 1862Hibbert, F., Hunte, K.P.J., (1983) J. Chem. Soc., Perkin Trans 2, p. 1895Staab, H.A., Saupe, T., (1988) Angew. Chem. Int. Ed. Engl., 27, p. 865Alder, R.W., (1989) Chem. Rev., 89, p. 1215Suarez, D., Menendez, J.A., Fuente, E., Montes-Moran, M.A., (2000) Angew. Chem. Int. Ed. Engl., 39, p. 1320Staab, H.A., Elbl-Weiser, K., Krieger, C., (2000) Eur. J. Org. Chem., 2, p. 327Eigen, M., (1964) Angew. Chem. Int. Ed. Engl., 3, p. 1Alder, R.W., Bryce, M.R., Goode, N.C., Miller, N., Owen, J., (1981) J. Chem. Soc., Perkin Trans 1, p. 2840Terrier, F., Halle, J.C., Pouet, M.J., Simonnin, M.P., (1986) J. Org. Chem., 51, p. 409Grott, R.L., Sikkema, D.J., (1976) Recl. Trav. Chim. Pays-Bas, 95, p. 10Staab, H.A., Saupe, T., Krieger, C., (1983) Angew. Chem. Int. Ed. Engl., 22, p. 731Wozniak, K., Raczynska, E.D., Korybut-Dasziewicz, B., (2000) Israel J. Chem., 39, p. 245Cleland, W.W., Kreevoy, M.M., (1994) Science, 264, p. 1887Warshel, A., Papazyan, A., (1995) Science, 269, p. 102Shan, S.O., Loh, S., Herschlag, D., (1995) Science, 272, p. 97Guthrie, J.P., (1996) Chem. Biol., 3, p. 163Gerlt, J.A., Kreevoy, M.M., Cleland, W.W., Frey, P.A., (1997) Chem. Biol., 4, p. 259Cassidy, C.S., Lin, J., Frey, P.A., (1997) Biochemistry, 36, p. 457

    Enantioselective Reductions Of Ketones Using Baker's Yeast [reduções Enantiosseletivas De Cetonas Utilizando-se Fermento De Pão]

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    Baker's yeast has been successful employed to reduce carbonyl compounds carrying appropriated substituents at distances under the electronic influence of the keto group. High yields and enantiomeric excess (ee) were obtained with 1,2-alkanedione, 1,2-alkanedione (2-O-methyloxime) and 1,3-alkanedione. Potential chiral building blocks were obtained and applied for stereoselective synthesis of valuable compounds. Evidence for a free radical chain process was obtained with baker's yeast reduction of a-iodoacetophenone using radical inhibitors.246893897Pasteur, L., (1862) C. R., Hebd. Seances Acad. Sci., 55, p. 28Brown, A.J., (1886) J. Chem. Soc., 49, p. 172Boutroux, L., (1880) C. R., Hebd. Seances Acad. Sci., 91, p. 236Bertrand, G., (1896) C. R., Hebd. Seances Acad. Sci., 122, p. 900Dumas, J.B., (1874) Ann. Chim. Phys., 5, p. 3Windisch, W., (1898) Chem. 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    Enantioselective reductions with enantiocomplementarity of α-haloacetophenones by Rhodotorula glutinis CCT 2182 and Geotrichum candidum CCT 1205 afforded the corresponding (R)- and (S)-halohydrins (halo = Cl, Br and I), respectively, in high chemical yields (89-99%) and enantiomeric excesses (92-99%). These halohydrins are potential chiral building blocks for the stereoselective syntheses of valuable compounds.200310404410Carvalho, M., Okamoto, M.T., Moran, P.J.S., Rodrigues, J.A.R., (1991) Tetrahedron, 47, pp. 2073-2080Sorrilha, A.E.P.M., Marques, M., Joekes, I., Moran, P.J.S., Rodrigues, J.A.R., (1992) Bioorg. Med. Chem. Lett., 2, pp. 191-196Sakai, T., Wada, K., Murakami, T., Kohra, K., Imajo, N., Ooga, Y., Tsuboi, S., Utaka, M., (1992) Bull. Chem. Soc. Jpn., pp. 631-638Besse, P., Sokoltchik, T., Veschambre, H., (1998) Tetrahedron Asymmetry, 9, pp. 4441-4457Wei, Z.-L., Li, Z.-Y., Lin, G.-Q., (1998) Tetrahedron, 54, pp. 13059-13072Barbiere, C., Bossi, L., D'Arrigo, P., Fantoni, G.P., Servi, S., (2001) J. Mol. Catal.: B Enzym., 11, pp. 415-421Ni, Y., Xu, J.-H., (2002) J. Mol. Catal.: B Enzym., 12, pp. 233-241Corey, E.J., Link, J.O., (1990) Tetrahedron Lett., 31, pp. 601-604Brenelli, E.C.S., Carvalho, M., Okubo, M.T., Marques, M., Moran, P.J.S., Rodrigues, J.A.R., Sorrilha, A.E.P.M., (1992) Indian J. Chem., 31 B, pp. 821-823Aleixo, L.M., Carvalho, M., Moran, P.J.S., Rodrigues, J.A.R., (1993) Bioorg. Med. Chem. Lett., 3, pp. 1637-1642Ohno, A., (1999) Rev. Heteroatom Chem., 20, pp. 29-68Nakamura, K., Fujii, M., Ida, Y., (2001) Tetrahedron Asymmetry, 12, pp. 3147-3153Salvi, N.A., Chattopadhyay, S., (2001) Tetrahedron, 57, pp. 2833-2839Comasseto, J.V., Omori, A.T., Andrade, L.H., Porto, A.L.M., (2003) Tetrahedron Asymmetry, 14, pp. 711-715Prelog, V., (1964) Pure Appl. Chem., 9, pp. 119-130noteNakamura, K., Inoue, Y., Matsuda, T., Ohno, A., (1995) Tetrahedron Lett., 36, pp. 6263-6266Tanner, D.D., Singh, H.K., Kharrat, A., Stein, A.R., (1987) J. Org. Chem., 52, pp. 2142-2146Tanner, D.D., Singh, H.K., (1986) J. Org. Chem., 51, pp. 5182-5186Tanner, D.D., Stein, A.R., (1988) J. Org. Chem., 53, pp. 1642-1646Tanner, D.D., Kharrat, A., (1988) J. Org. Chem., 53, pp. 1646-1650Smolen, J.M., Weber, E.J., Tratnyek, P.G., (1999) Environ. Sci. Technol., 33, pp. 440-445Ohno, A., Kito, N., (1972) Chem. Lett., pp. 369-372Ohno, A., Yamamoto, H., Oka, S., (1981) J. Am. Chem. Soc., 103, pp. 2041-2045http://www.fat.org.br/, Rua Latino Coelho 1301, 13087-010 Campinas-SP, Brazi
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