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116 Rev. Soc. Quím. Méx. Vol. 47, Núm. 2 (2003) Jorge A. Mendoza et al. 13. Zhuo, J.-C. Magn. Reson. Chem. 1998, 36, 565-572. 14. (a) Fleming, I. Frontier Orbitals and Organic Chemical Reactions. John Wiley & Sons, Chichester, 1976. (b) Houk, K. N. Acc. Chem. Res. 1975, 8, 361-369. (c) Eisenstein, O.; Lefour, J. M.; Anh, N. T.; Hudson, R. F. Tetrahedron 1977, 33, 523-531. (d) Spíno, C.; Pesant, M. Dory, Y. Angew. Chem., Int. Ed. 1998, 37, 3262-3265. 15. (a) Carruthers, W. Cycloaddition Reactions in Organic Synthesis. Pergamon Press, Oxford, 1990, 269-331. (b) Houk, K. N.; Chang, Y.-M.; Strozier, R. W.; Caramella, P. Heterocycles 1977, 7, 793- 799. (c) Huisgen, R., in: 1,3-Dipolar Cycloaddition Chemistry, Vol. 1, Padwa, A., Ed., Wiley-Interscience, New York, 1984. (d) Jarosková, L.; Fisera, L.; Matejková, I.; Ertl, P.; Prónayová, N. Monatsh. Chem. 1994, 125, 1413-1425. (e) Houk, K. N.; Sims, J.; Duke, Jr., R. E.; Strozier, R. W.; George, J. K. J. Am. Chem. Soc. 1973, 95, 7287-7301. 16. (a) Sauer, J.; Sustmann, R. Angew. Chem., Int. Ed. Engl. 1980, 19, 779-807. (b) Anh, N. T.; Canadell, E.; Eisenstein, O. Tetrahedron 1978, 34, 2283-2288. 17. (a) Exner, O. J. Phys. Org. Chem. 1999, 12, 265-274. (b) Charton, M. J. Phys. Org. Chem. 1999, 12, 275-282. (c) Galkin, V. I. J. Phys. Org. Chem. 1999, 12, 283-288. 18. Zhuo, J.-C.; Schenk, K. Helv. Chim. Acta 1997, 80, 2137-2147. 19. Allen, F. H.; Kennard, E.; Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1-S19. 20. (a) Fox, M. A.; Cardona, R.; Kiwiet, N. J. J. Org. Chem. 1987, 52, 1469-1474. (b) Bachler, V.; Mark, F. Theoret. Chim. Acta 1976, 43, 121-135. (c) Tripathy, R.; Franck, R. W.; Onan, K. D. J. Am. Chem. Soc. 1988, 110, 3257-3262. (d) Padwa, A.; Kline, D. N.; Koehler, K. F.; Matzinger, M.; Venkatramanan, M. K. J. Org. Chem. 1987, 52, 3909-3917. 21. Kahn, S. D.; Pau, C. F.; Overman, L. E.; Hehre, W. J. J. Am. Chem. Soc. 1986, 108, 7381-7396. 22. The authors have deposited the atomic coordinates for this structure with the Cambridge Crystallographic Data Centre. The coordinates can be obtained, on request, from the Director Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK. 23. SHELXTL, v. 5.03, Siemens Energy & Automation, Germany, 1995. 24. Calculated with Gaussian 94, Revision E.2: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Pittsburgh, PA, 1995; and Mac- Spartan, v. 1.0, WaveFunction Inc., 18401 VonKarman, Suite 370, Irvine, CA 92715. 25. Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902-3909.
Revista de la Sociedad Química de México, Vol. 47, Núm. 2 (2003) 117-123 Investigación 2D 1 H and 13 C NMR from the adducts of the dichloro carbene addition to β-ionone. The role of the catalyst on the phase transfer reaction Eduardo Díaz, *a José Luis Nava, a Héctor Barrios, a David Corona, a Ángel Guzmán, a Ma. de Lourdes Muciño, b and Aydeé Fuentes b a Instituto de Química, Universidad Nacional Autónoma de México. Circuito Exterior, Ciudad Universitaria, Coyoacán 04510 México D.F. b Facultad de Química, Universidad Autónoma del Estado de México, Toluca, Estado de México. Recibido el 9 de diciembre del 2002; aceptado el 26 de febrero del 2003 En homenaje al Dr. Alfonso Romo de Vivar Abstract. Several haloderivatives were synthesized from β-ionone using CHCl 3 , NaOH and selected tetralkyl ammonium halide. 2D NMR and X-ray single crystal analysis of the products are reported. Keywords: Addition of dichlorocarbenes to β-Ionone, phase transfer addition, formation of 1,1 dichlorocyclopropanes. 1 H and 13 C NMR. Resumen. Algunos haloderivados fueron sintetizados a partir de β- ionona usando cloroformo, hidróxido de sodio y halogenuros de tetralquilamonio selectos. Se informan los análisis por 2D RMN y rayos X de los productos. Palabras clave: Adición de diclorocarbenos a β-ionona, adición de transferencia de fase, formación de 1,1 diclorociclopropanos. RMN de 1 H y 13 C. Introduction A large number of C13-compounds formed by oxidative cleavage of carotenoids have been isolated from tobacco [1] and marine sponges [2] or their derivatives, originated from α and β ionones (1' and 1). In the same way, some other secondary metabolites as 4-oxomegastigmenos, important compounds for their excellent flavor characteristics are also formed in the tobacco plant from α and β ionones. Other derivatives from ionones, isolated from rabbit urine and from the secretion of the anal gland of the red fox have been obtained when α-ionone was photo-oxygenated [3, 4]. The synthesis of several damascones [5] and abscisic acids [6, 7] using readily available and inexpensive ionones as raw material encourages us to perform a reaction leading to some new functionalized and useful unsaturated compounds. Results and discussion The present paper deals with the synthesis and structure elucidation of new representatives of this group of compounds. We describe here the products obtained when β-ionone was treated with CHCl 3 , NaOH, using as catalyst different tetralkyl quaternary ammonium salts looking to improve yields and versatility of the reaction under phase transfer conditions. Likewise, the reaction of carbenes with terpenes provides a simple means of examining the stereochemistry and regioselectivity of addition of such species to a variety of double bonds. It has been reported that in phase transfer dihalocarbene addition, stereochemistry and regioselectivity can be controlled by varying the catalyst [8-11]. Phase transfer reactions are known to be somewhat dependent on the exact reaction conditions and the formation of products apparently derived from trihalogenomethyl anion or dihalogen carbene can be controlled by varying the catalyst [9]. Some years ago [12], our group reported β-Ionone when treated under CHCl 3 , NaOH and triethylbenzyl ammonium chloride (TEBAC) yield two furenones 2 and 3 which were isolated in low yield. Their structures were well supported by 2D NMR as well as x-ray crystallographic analysis [13]. On the mechanism of formation of these compounds it was assumed an initial chemoselective adduct formation on the β-ionone to generate the epoxide, which is rapidly transformed to an intermediate dichloro ether which is hydrolized to a γ-lactone where the presence of atmospheric oxygen during the reaction induced free radical dimerization [12]. The low yield observed in this reaction as well as the new findings about the phase transfer reactions encourage us to undertake the study of the dichlorocarbene addition to β- ionone using different quaternary ammonium catalyst. Under the new catalyst selection, the usual γ-lactone derivatives (2 and 3) were isolated together with several new compounds which display structure versatility and in addition allowed us to improve yields, as well as products ratio of the obtained adducts. Structures of compounds 2 and 3 were well discussed in our previous report and they will not be focused here.
Page 5 and 6: REVISTA de la SOCIEDAD QUÍMICA d e
Page 7 and 8: Editorial La investigación cientí
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Two New Oleanolic Acid Saponins fro
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Two New Oleanolic Acid Saponins fro
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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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