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Methyl 8a-Formyloxy-labd-13Z-en-15-oate [(-)-(2Z)-5-((1R,2R,4aS,8aS)-2-Formyloxy-2,5,5,8a-tetramethyldecahydro-1-naphthalenyl)-3-methyl- 2-pentenoic Acid Methyl Ester]

Departamento de Química Inorgánica y Orgánica, Facultad de Ciencias Experimentales, Universidad de Jaén, 23071 Jaén, Spain
*
Author to whom correspondence should be addressed.
Molbank 2003, 2003(1), M302; https://doi.org/10.3390/M302
Received: 12 December 2001 / Accepted: 19 September 2002 / Published: 8 March 2003

Excerpt

Note: In lieu of an abstract, this is an excerpt from the first page.

A sample (0.03 mL, 0.45 mmol) of formic acid-acetic anhydride mixture (FAM), prepared from Ac2O and formic acid as described in the literature [1], was added to the alcohol 1 [2] (29 mg, 0.09 mmol) at 10 ºC.[...]
Keywords: Diterpenes, labdanes, formylation, FAM, tertiary alcohol Diterpenes, labdanes, formylation, FAM, tertiary alcohol
Molbank 2003 m302 i001
A sample (0.03 mL, 0.45 mmol) of formic acid-acetic anhydride mixture (FAM), prepared from Ac2O and formic acid as described in the literature [1], was added to the alcohol 1 [2] (29 mg, 0.09 mmol) at 10 °C. After stirring for 48 h at room temperature, water (10 mL) was added and the mixture extracted with Et2O (3×25 mL). The combined organic layers were washed with 2N HCl (25 mL), saturated aq. Na2CO3 (25 mL) and brine (25 mL). The organic phase was dried over anhydrous Na2SO4 and the solvent evaporated under reduced pressure to yield a residue (29 mg) which was purified by flash chromatography on silica gel, using a 4:1 hexane/Et2O mixture as eluent, to give the title compound 2 (19 mg, 0.05 mmol, 60%).
Mp: 58.0-59.6 °C (white crystals, from hexane).
[a]D = -12.7° (c 1.02 cg·mL-1, CHCl3).
IR (KBr, n, cm-1): 1728, 1193 (OOCH), 1705, 1241, 1171 (COOMe), 1649, 875 (C=C).
1H NMR (300 MHz, CDCl3, d, ppm): 0.77 (3H, s, Meb-4), 0.82 (3H, s, Me-10), 0.86 (3H, s, Mea-4), 1.49 (3H, s, Me-8), 1.88 (3H, d, J=1.4 Hz, Me-13), 0.99-1.88 (13H, m, H-1,2,3,5,6,7a,9,11), 2.53 (1H, dt, J=12.5 Hz, 3.3 Hz, Hb-7), 2.59-2.76 (2H, m, H-12), 3.65 (3H, s, OMe), 5.60 (1H, br s, H-14), 8.04 (1H, s, OOCH).
13C NMR (75 MHz, CDCl3, d, ppm): 39.36* (C-1), 18.35 (C-2), 41.80 (C-3), 33.13 (C-4), 55.52 (C-5), 20.01 (C-6), 39.32* (C-7), 89.08 (C-8), 58.91 (C-9), 39.53 (C-10), 24.10 (C-11), 36.13 (C-12), 160.49 (C-13), 115.44 (C-14), 166.53 (C-15), 25.16 (C-16), 21.24 (C-17), 33.29 (C-18), 21.42 (C-19), 15.69 (C-20), 50.78 (OMe), 160.65 (OOCH) (* these signals may be interchanged).

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

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 Notes

  1. Strazzolini, P.; Giumanini, A. G.; Cauci, S. Acetic Formic Anhydride. A Review. Tetrahedron 1990, 46, 1081–1118. [Google Scholar] [CrossRef]
  2. Urones, J. G.; Basabe, P.; Marcos, I. S.; González, J. L.; Jiménez, V.; Sexmero, M. J.; Lithgow, A. M. Ambergris Compounds from Labdanolic Acid. Tetrahedron 1992, 48, 9991–9998. [Google Scholar] [CrossRef]
  • Sample availability: Available from the authors and from MDPI
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