 2003, M299 www.molbank.org 8Formyllabdanolic Acid ()(3S)5((1,2,4a,8a)2Formyloxy2,5,5,8atetramethyldecahydro1naphthalenyl)3 methylpentanoic Acid Juan M. Castro, Sofia Salido, Joaquin Altarejos*, Manuel *ogueras and Adolfo Sanchez Departamento de Química Inorgánica y Orgánica, Facultad de Ciencias Experimentales, Universidad de Jaén, 23071 Jaén, Spain Tel.: 3409530002743, fax: 3409530012141, E0mail: jaltare@ujaen.es              ! Keywords: Diterpenes, labdanes, labdanolic acid, Cistus ladaniferus, formylation, FAM, tertiary alcohol A sample (0.85 mL, 6.5 mmol) of formic acid0acetic anhydride mixture (FAM), prepared from Ac 2 O and formic acid as described in the literature [1], was added to the alcohol 1 [2](255 mg, 0.79 mmol) at 10 ºC. After stirring for 48 h at room temperature, water (10 mL) was added and the mixture extracted with Et 2 O (3×25 mL). The combined organic layers were washed with 2N HCl (25 mL), saturated aq. Na 2 CO 3 (25 mL) and brine (25 mL). The organic phase was dried over anhydrous Na 2 SO 4 and the solvent evaporated under reduced pressure to yield a residue (258 mg) which was purified by flash chromatography on silica gel, using a 3:2 hexane/EtOAc mixture as eluent, to give the pure title compound 2 (180 mg, 0.51 mmol, 65%). Mp: 102.40105.5 ºC (pale yellow crystals, from hexane). [a] D = 033.7º (c 1.2 cg·mL 01 , CHCl 3 ). IR (neat, n, cm 01 ): 360002500, 1719 (COOH), 1719, 1200, 1180 (OOCH). 1 H NMR (300 MHz, CDCl 3 , d, ppm): 0.79 (3H, s, Me b 04), 0.84 (3H, s, Me010), 0.87 (3H, s, Me a 04), 0.98 (3H, d, J=6.6 Hz, Me013), 1.49 (3H, s, Me08), 0.9902.00 (16H, m, H01,2,3,5,6,7a,9,11,12,13), 2.15 (1H, dd, J=15.0 Hz, 8.0 Hz, H014), 2.36 (1H, dd, J=15.0 Hz, 5.9 Hz, H'014), 2.57 (1H, dt, J=12.3 Hz, 3.2 Hz, H b 07), 8.00 (1H, s, OOCH). 13 C NMR (75 MHz, CDCl 3 , d, ppm): 39.46 (C01), 18.23 (C02), 41.78 (C03), 33.05 (C04), 55.51 (C05), 19.98 (C06), 39.36 (C07), 89.17 (C08), 58.91 (C09), 39.42 (C010), 22.99 (C011), 39.63 (C012), 30.88 (C013), 41.44 (C014), 179.48 (C015), 19.63 (C016), 21.09 (C017), 33.24 (C018), 21.37 (C019), 15.65 (C020), 160.61 (OOCH). Acknowledgements: We wish to thank the Junta de Andalucía for financial support and the Ministerio de Educación, Cultura y Deporte for a Fellowship to J. M. Castro. References and *otes 80Formyl0labdanolic Acid http://www.mdpi.org/molbank/molbank2003/m0299.htm 1 von 2 31.03.2009 12:50