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114 Rev. Soc. Quím. Méx. Vol. 47, Núm. 2 (2003) Jorge A. Mendoza et al. (Z)-4-Methylsulfanyl-3-(p-nitrobenzoyloxy)-3-buten-2-one (10a). According to method A with 0.291 g (4.16 mmol) of 9a, afforded 0.76 g (85 %) of 10a as a pale yellow oil: R f 0.21 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1746, 1675, 1589, 1530, 1347, 1248, 1093, 895 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 2.34 (s, 3H, CH 3 CO), 2.50 (s, 3H, CH 3 S), 7.39 (s, 1H, HC=), 8.32-8.34 (m, 4H, Ar-H); 13 C NMR (75.4 MHz, CDC l3 ) δ 17.3 (CH 3 S), 24.7 (CH 3 CO), 123.7, 131.4, 134.1, 136.9 (C-4), 142.3 (C-3), 151.1, 161.7 (ArCO 2 ), 187.1 (CH 3 CO); MS (70 eV) 281 (M + , 4), 150 (100), 134 (22), 120 (15), 104 (22), 92 (11), 76 (14). (Z)-4-Ethylsulfanyl-3-(p-nitrobenzoyloxy)-3-buten-2-one (10b). According to method A with 0.349 g (4.16 mmol) of 9b, afforded 0.84 g (90 %) of 10b as a pale yellow oil. According to method B with 0.258 g (4.16 mmol) of 9d, gave 0.73 g (78 %) of 10b. According to method C with 0.289 g (4.67 mmol) of 9d, furnished 0.83 g (74%) of 10b: R f 0.22 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1746, 1675, 1588, 1529, 1423, 1348, 1275, 1246, 1217, 1049, 1013 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 1.43 (t, J = 7.1 Hz, 3H, CH 3 CH 2 S), 2.35 (s, 3H, CH 3 CO), 2.92 (q, J = 7.1 Hz, 3H, CH 3 CH 2 S), 7.49 (s, 1H, HC=), 8.45-8.47 (m, 4H, Ar-H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 15.4 (CH 3 CH 2 S), 24.7 (CH 3 CO), 28.4 (CH 3 CH 2 S), 123.6, 131.4, 134.1, 135.1 (C-4), 142.5 (C-3), 151.0, 161.7 (ArCO 2 ), 187.1 (CH 3 CO). Anal. Calcd for C 13 H 13 NO 5 S: C, 52.87; H, 4.44. Found: C, 52.80; H, 4.68. (Z)-4-Isopropylsulfanyl-3-(p-nitrobenzoyloxy)-3-buten-2- one (10c). According to method A with 0.408 g (4.16 mmol) of 9c, afforded 0.88 g (90 %) of 10c as a pale yellow oil. According to method B with 0.358 g (4.16 mmol) of 9e, gave 0.80 g (81 %) of 10c. According to method C with 0.402 g (4.67 mmol) of 9e, furnished 0.90 g (77 %) of 10c: R f 0.30 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1746, 1674, 1587, 1530, 1453, 1427, 1348, 1314, 1218, 1157, 1092, 1015, 958, 898, 870, 847 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 1.38 (d, J = 7.3 Hz, 6H, (CH 3 ) 2 CHS), 2.35 (s, 3H, CH 3 CO), 3.33 (sept, J = 7.3 Hz, 3H, (CH 3 ) 2 CHS), 7.50 (s, 1H, HC=), 8.38-8.36 (m, 4H, Ar-H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 23.4 ((CH 3 ) 2 CHS), 24.5 (CH 3 CO), 38.4 ((CH 3 ) 2 CHS), 123.4, 131.1, 133.9, 134.1 (C-4), 141.9 (C-3), 150.7, 161.5 (ArCO 2 ), 187.0 (CH 3 CO). Anal. Calcd for C 14 H 15 NO 5 S: C, 54.36; H, 4.89. Found: C, 54.30; H, 5.00. (Z)-4-tert-Butylsulfanyl-3-(p-nitrobenzoyloxy)-3-buten-2- one (10d). According to method B with 0.375 g (4.13 mmol) of 9f, afforded 0.84 g (82 %) of 10d as a pale yellow oil. According to method C with 0.514 g (4.67 mmol) of 9f, furnished 0.86 g (70%) of 10d: R f 0.26 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1744, 1673, 1584, 1529, 1349, 1248, 1093, 769, 751 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 1.48 (s, 9H, (CH 3 ) 3 CS), 2.35 (s, 3H, CH 3 CO), 7.60 (s, 1H, HC=), 8.33 (br s, 4H, Ar- H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 24.8 (CH 3 CO), 31.1 ((CH 3 ) 3 CS), 45.7 ((CH 3 ) 3 CS), 123.7, 131.4, 131.6 (C-4), 134.2, 142.3 (C-3), 151.0, 162.4 (ArCO 2 ), 198.8 (CH 3 CO). Anal. Calcd for C 15 H 17 NO 5 S: C, 55.71; H, 5.30. Found: C, 55.50; H, 5.30. (Z)-4-Benzylsulfanyl-3-(p-nitrobenzoyloxy)-3-buten-2-one (10e). According to method B with 0.516 g (4.13 mmol) of 9g, afforded 1.02 g (90 %) of 10e as a pale yellow oil. According to method C with 0.579 g (4.67 mmol) of 9g, furnished 1.18 g (87 %) of 10e: R f 0.28 (hexane / EtOAc, 8:2); IR (CH 2 Cl 2 ) 1740, 1677, 1606, 1530, 1348, 1248, 1093 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 2.25 (s, 3H, CH 3 CO), 4.08 (s, 2H, CH 2 Ph), 7.27-7.46 (m, 6H, HC=, Ph-H), 8.28-8.39 (m, 4H, Ar-H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 24.7 (CH 3 CO), 38.0 (CH 2 Ph), 123.7, 128.2, 129.0, 129.1, 131.4, 134.0, 134.2 (C- 4), 136.7, 142.4 (C-3), 150.9, 161.7 (ArCO 2 ), 187.1 (CH 3 CO). (Z)-4-(4-Bromophenylsulfanyl)-3-(4-nitrobenzoyloxy)-3- buten-2-one (10f). According to method B with 0.786 g (4.16 mmol) of 9h, afforded 1.29 g (96 %) of 10f as pale yellow crystals. According to method C with 0.883 g (4.67 mmol) of 9h, furnished 1.45 g (91 %) of 10f: mp 174-175 °C; R f 0.16 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1747, 1679, 1531, 1419, 1348, 1243, 1090, 1008 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 2.35 (s, 3H, CH 3 CO), 7.36-7.40 (m, 2H, Ar-H), 7.46 (s, 1H, HC=), 7.51-7.55 (m, 2H, Ar-H), 8.30-8.38 (m, 4H, Ar-H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 24.9 (CH 3 CO), 123.6, 123.7, 130.8, 131.5, 132.9, 133.1, 133.7, 134.1 (C-4), 142.6 (C-3), 151.2, 161.7 (ArCO 2 ), 187.3 (CH 3 CO). Anal. Calcd for C 17 H 12 BrNO 5 S: C, 48.36; H, 2.86; N 3.32; S, 7.58. Found: C, 48.04; H, 2.80; N, 3.29; S, 7.41. (Z)-4-(4-Methoxyphenylsulfanyl)-3-(4-nitrobenzoyloxy)-3- buten-2-one (10g). According to method B with 0.582 g (4.16 mmol) of 9i, afforded 0.95 g (80 %) of 10g as pale yellow crystals. According to method C with 0.654 g (4.67 mmol) of 9i, furnished 1.25 g (93 %) of 10g: mp 122-123 °C; R f 0.20 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1743, 1674, 1592, 1546, 1531, 1492, 1421, 1346, 1264, 1093 cm –1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 2.33 (s, 3H, CH 3 CO), 3.82 (s, 3H, MeO), 6.88-6.94 (m, 2H, Ar-H), 7.44-7.49 (m, 2H, Ar-H), 7.45 (s, 1H, HC=), 8.34 (s, 4H, Ar-H); 13 C NMR (75.4 MHz, CDCl 3 ) δ 24.8 (CH 3 CO), 55.4 (CH 3 O), 115.3, 122.0, 123.6, 131.5, 134.0, 134.2, 137.2 (C-4), 141.5 (C-3), 150.9, 160.7, 161.7 (ArCO 2 ), 187.2 (CH 3 CO). Anal. Calcd for C 18 H 15 NO 6 S: C, 57.90; H, 4.05; N, 3.75; S, 8.59. Found: C, 58.08; H, 4.12; N 3.74; S, 8.70. (Z)-4-(4-Methylphenylsulfanyl)-3-(4-nitrobenzoyloxy)-3- buten-2-one (10h). According to method B with 0.516 g (4.16 mmol) of 9j, afforded 0.92 g (81 %) of 10h as pale yellow crystals. According to method C with 0.58 g (4.67 mmol) of 9j, furnished 1.15 g (90 %) of 10h: mp 113-115 °C; R f 0.22 (hexane/EtOAc, 8:2); IR (CH 2 Cl 2 ) 1747, 1677, 1589, 1531, 1348, 1091, 897, 847, 807 cm –1 ; 1 H NMR (500 MHz, CDCl 3 ) δ 2.33 (s, 3H, CH 3 CO), 2.37 (s, 3H, MeAr), 7.20-7.22 (m, 2H, Ar-H), 7.39-7.41 (m, 2H, Ar-H), 7.50 (s, 1H, HC=), 8.34 (s, 4H, Ar-H); 13 C NMR (125 MHz, CDCl 3 ) δ 21.1 (CH 3 Ar), 24.8 (CH 3 CO), 123.7, 128.2, 130.5, 131.5, 131.9, 134.0, 136.3
Synthesis, Structural, and Theoretical Study of New β-Heterosubstituted Captodative Olefins 1-Acetylvinyl Arenecarboxylates 115 (C-4), 138.5, 141.9 (C-3), 151.0, 161.7 (ArCO 2 ), 187.3 (CH 3 CO). Anal. Calcd for C 18 H 15 NO 5 S: C, 60.49; H, 4.23. Found: C, 60.27; H, 4.50. Single-Crystal X-Ray Crystallography [22]. Olefin 10f was obtained as pale yellow crystals. These were mounted in glass fibers. Crystallographic measurements were performed on a Siemens P4 diffractometer with Mo Kα radiation (λ = 0.7107 Å; graphite monochromator) at room temperature. Two standard reflections were monitored periodically; they showed no change during data collection. Unit cell parameters were obtained from least-squares refinement of 26 reflections in the range 2 < 2Θ < 20°. Intensities were corrected for Lorentz and polarization effects. No absorption correction was applied. Anisotropic temperature factors were introduced for all nonhydrogen atoms. Hydrogen atoms were placed in idealized positions and their atomic coordinates refined. Unit weights were used in the refinement. The structure was solved using SHELXTL on a personal computer [23]. Data of 10f: Formula: C 17 H 12 BrNO 5 S; molecular weight: 422.25; cryst. syst.: monoclinic; space group: P2 1 /c; unit cell parameters: a, 6.4121 (9), b, 12.8041 (11), c, 20.998 (2) (Å); α, 90, β, 94.884 (9), γ, 90 (deg); temp. (°K): 293 (2); Z: 4; No. of reflections collected: 4641; no. of independent reflections: 3335; no. of observed reflections: 3290; R: 0.0429; GOF: 1.012. Calculations. The ab initio SCF/HF calculations were carried out with the 6-31G* basis sets using Gaussian 94 [24] and MacSpartan [24]. Geometries were fully optimized by the AM1 semiempirical method [25] and these were employed as starting point for optimization, at the 6-31G* level. Acknowledgments We thank Fernando Labarrios for his help in spectrometric measurements. J.T. would like to acknowledge DEPI/IPN (Grants 921769 and 200410) and CONACyT (Grants 1570P and 32273-E) for financial support. H.A.J.-V. thanks CONACyT (Grant 3251P) for financial support. J.M. and R.H. are grateful to CONACyT (Grants 86038 and 91187) for graduate fellowships, to PIFI-IPN program for a scholarship, and to the Ludwig K. Hellweg Foundation for a partial scholarship. J.L. is grateful to Secretaría de Relaciones Exteriores, México (Grant DAC-III 811.5/(510)/137) for a research fellowship. J.T. and H.A.J.-V. are fellows of the EDD/IPN and COFAA/IPN programs. References and notes 1. (a) Viehe, H. G.; Janousek, Z.; Merényi, R.; Stella, L. Acc. Chem. Res. 1985, 18, 148-154. (b) Cativiela, C.; Fraile, J. M.; García, J. I.; Mayoral, J. A.; Pires, E.; Royo, A. J.; Figueras, F.; de Ménorval, L. C. Tetrahedron 1993, 49, 4073-4084. (c) Boucher, J.-L.; Stella, L. Tetrahedron 1986, 42, 3871-3885. (d) Seerden, J.-P. G.; Scheeren, H. W. Tetrahedron Lett. 1993, 34, 2669-2672. (e) Döpp, D.; Libera, H. Tetrahedron Lett. 1983, 24, 885-888. (f) Rulev, A. Y. Russ. Chem. Rev. 2002, 71, 195-221. (g) Seneci, P.; Leger, I.; Souchet, M.; Nadler, G. Tetrahedron 1997, 53, 17097- 17114. (h) Moody, C. J.; Hughes, R. A.; Thompson, S. P.; Alcaraz, L. Chem. Commun. 2002, 1760-1761. (i) Kozmin, S. A.; Iwama, T.; Huang, Y.; Rawal, V. H. J. Am. Chem. Soc. 2002, 104, 4628-4641. (j) Ferreira, P. M. T.; Maia, H. L. S.; Monteiro, L. S. Tetrahedron Lett. 2002, 43, 4491-4493. (k) Ferreira, P. M. T.; Maia, H. L. S.; Monteiro, L. S. Tetrahedron Lett. 2002, 43, 4495-4497. (l) Huang, C.-G.; Chang, B.-R.; Chang, N.-C. Tetrahedron Lett. 2002, 43, 2721-2723. 2. (a) Reyes, A.; Aguilar, R.; Muñoz, A. H.; Zwick, J.-C.; Rubio, M.; Escobar, J.-L.; Soriano, M.; Toscano, R.; Tamariz, J. J. Org. Chem. 1990, 55, 1024-1034. (b) Aguilar. R.; Reyes. A.; Tamariz, J.; Birbaum, J.-L. Tetrahedron Lett. 1987. 28. 865-868. (c) García de Alba, O.; Chanona, J.; Delgado, F.; Zepeda, G.; Labarrios, F.; Bates, R. W.; Bott, S.; Juaristi, E.; Tamariz, J. Anal. Quím., Int. Ed. 1996, 92, 108-117. 3. (a) Nagarajan, A.; Zepeda, G.; Tamariz, J. Tetrahedron Lett. 1996, 37, 6835-6838. (b) Jiménez, R.; Pérez, L.; Tamariz, J.; Salgado, H. Heterocycles 1993, 35, 591-598. (c) Herrera, R.; Nagarajan, A.; Morales, M. A.; Méndez, F.; Jiménez-Vázquez, H. A.; Zepeda, L. G.; Tamariz, J. J. Org. Chem. 2001, 66, 1252- 1263. 4. (a) Andrade, R. M.; Muñóz, A. H.; Tamariz, J. Synth. Commun. 1992, 22, 1603-1609. (b) Orduña, A.; Zepeda, G.; Tamariz, J. Synthesis 1993, 375-377. (c) Dienes, Z.; Vogel, P. J. Org. Chem. 1996, 61, 6958-6970. (d) Ochoa, M. E.; Arias, A. S.; Aguilar, R.; Delgado, F.; Tamariz, J. Tetrahedron 1999, 55, 14535-14546. (e) Aguilar, R.; Reyes, A.; Orduña, A.; Zepeda, G.; Bates, R. W.; Tamariz, J. Rev. Soc. Quím. Méx. 2000, 44, 91-96. 5. Herrera, R.; Jiménez-Vázquez, H. A.; Modelli, A.; Jones, D.; Söderberg, B. C.; Tamariz, J. Eur. J. Org. Chem. 2001, 4657- 4669. 6. Peralta, J.; Bullock, J. P.; Bates, R. W.; Bott, S.; Zepeda, G.; Tamariz, J. Tetrahedron 1995, 51, 3979-3996. 7. (a) Rappoport, Z., Ed., The Chemistry of Enamines. Wiley, Chichester, 1994. (b) Greenhill, J. V. Chem. Soc. Rev. 1977, 6, 277-294. (c) Granik, V. G. Russ. Chem. Rev. 1984, 53, 383-404. 8. (a) Scott, K. R.; Edafiogho, I. O.; Richardson, E. L.; Farrar, V. A.; Moore, J. A.; Tietz, E. I.; Hinko, C. N.; Chang, H.; El-Assadi, A.; Nicholson, J. M. J. Med. Chem. 1993, 36, 1947-1955. (b) Kesten, S. J.; Degnan, M. J.; Hung, J.; McNamara, D. J.; Ortwine, D. F.; Uhlendorf, S. E.; Werbel, L. M. J. Med. Chem. 1992, 35, 3429-3447. 9. For some recent examples: (a) Bhathia, G. S.; Lowe, R. F.; Pritchard, R. G.; Stoodley, R. J. Chem. Commun. 1997, 1981- 1982. (b) Abbiati, G.; Clerici, F.; Gelmi, M. L.; Gambini, A.; Pilati, T. J. Org. Chem. 2001, 66, 6299-6304. (c) Clerici, F.; Gelmi, M. L.; Pocar, D.; Pilati, T. Tetrahedron: Asymmetry 2001, 12, 2663-2669. (d) Buñuel, E.; Gil, A. M.; Díaz-de-Villegas, M. D.; Cativiela, C. Tetrahedron 2001, 57, 6417-6427. (e) Clerici, F.; Gelmi, M. L.; Gambini, A.; Nava, D. Tetrahedron 2001, 57, 6429-6438. (f) Maekawa, K.; Igarashi, T.; Kubo, K.; Sakurai, T. Tetrahedron 2001, 57, 5515-5526. (g) Caine, D. Tetrahedron 2001, 57, 2643-2684. (h) Stanovnik, B.; Svete, J. Synlett 2000, 1077-1091. (i) Yonehara, K.; Ohe, K.; Uemura, S. J. Org. Chem. 1999, 64, 9381-9385. 10. (a) Sustmann, R. Tetrahedron Lett. 1971, 2721-2724. (b) Houk, K. N.; Sims, J.; Watts, C. R.; Luskus, L. J. J. Am. Chem. Soc. 1973, 95, 7301-7315. 11. Jiménez-Vázquez, H. A.; Ochoa, M. E.; Zepeda, G.; Modelli, A.; Jones, D.; Mendoza, J. A.; Tamariz, J. J. Phys. Chem. A 1997, 101, 10082-10089. 12. (a) Guseinov, F. I.; Yudina, N. A.; Burangulova, R. N.; Ryzhikova, T. Ya.; Valliullina, R. Zh. Chem. Heterocyclic Comp. 2002, 38, 496-497. (b) Toplak, R.; Svete, J.; Stanovnik, B.; Grdadolnik, S. G. J. Heterocyclic Chem. 1999, 36, 225-235. (c) Pizzioli, L.; Ornik, B.; Svete, J.; Stanovnik, B. Helv. Chim. Acta 1998, 81, 231-235.
Page 5 and 6: REVISTA de la SOCIEDAD QUÍMICA d e
Page 7 and 8: Editorial La investigación cientí
Page 9 and 10: Editorial 103 Jacobo Gómez Lara (1
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Page 25 and 26: 2D 1 H and 13 C NMR from the adduct
Page 31 and 32: Reactivity of IrH 2 {C 6 H 3 -2,6-(
Page 35 and 36: The Use of N,N’-Di[α-phenylethyl
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Page 39 and 40: Preparation of 11-Hydroxylated 11,1
Page 47 and 48: Chemical Composition and Antimicrob
Page 51 and 52: Sesquiterpene Lactone Sequestration
Page 53 and 54: Mechanism of Glutamate Neurochemist
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Page 59 and 60: Cumarinas presentes en especies del
Page 63 and 64: Preparación de materiales mesoporo
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Page 67 and 68: New Eremophilanoids from the Roots
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165 Rev. Soc. Quím. Méx. Vol. 47,
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Revista de la Sociedad Química de
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Isolation and Chemical Transformati
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Isolation and Chemical Transformati
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Two New Oleanolic Acid Saponins fro
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Two New Oleanolic Acid Saponins fro
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Análisis isobolográfico de la int
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185 Rev. Soc. Quím. Méx. Vol. 47,
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Cytotoxic Evaluation of a Series of
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Cytotoxic Evaluation of a Series of
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El análisis conformacional a la lu
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Synthesis and properties of 2-Diazo
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Synthesis and properties of 2-Diazo
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Estudio fitoquímico de Salvia urua
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