Riassunto
L'isolamento dallaSpongia officinalis di otto C21 monofuranoterpeni, strettamente correlati alla furospongina-1 (1), il componente terpe ico più abbondante della stessa spugna, per quattro dei quali si dimostrano le strutture di γ-idrossi-α,β-butenolidi (2–5) e per gli altri quattro, le strutture di β,γ-epossibutenolidi (6–9), sembra rilevante in connessione col problema della ossidrilazione dei substrati aromatici in vivo.
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Literatur
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The mixture of the acetates of (2) and (3) has the following spectra features: MS,m/e 446 (M+), 386, 326; IR,v max 1770 and 1728 cm−1; NMR, δ 6.78 (2H, broad singlet, protons of the butenolide moiety)4, 2.1 and 1.92 (each 3H singlets, CH3CO−).
It should be noted that the peak atm/e 150 originates by cleavage of the 10, 11-bond and H transfer; the same strong peak is equally apparent in the mass spectrum of furospongin-1 (1)1.
The mixture of α,β-unsaturated γ-lactone acetates derived from (2) and (3) has the following properties: MS, M+/e 388; NMR, δ 7.10 (1H, t, J=2Hz, −CH=C−C=O) and 4.68 (2H, narrow multiplet, −CH2−O−C=O)4 coupled to each other, and confirmed by decoupling experiments; IRv max 1750 (α, β-unsaturated γ-lactone), 1730 (acetate) and 1690 (C=C).
H. Minato andT. Nagasaki, J. chem. Soc. (C)1966, 377.
The mixture of α,β-unsaturated γ-lactones, obtained by NaBH4 reduction of the mixture of lactols (4) and (5), was also characterized as the acetates: MS, M+/e 388; NMR δ 5.74 (1H, narrow multiplet, C=CH−C=O)10 and 4.61 (2H, narrow multiplet, −CH2−C=O); IR,v max 1750 (α, β-unsaturated γ-lactone), 1730 (acetate) and 1685 (C=C).
N. S. Bhacca, L. F. Johnson andJ. N. Shoolery,NMR Spectra Catalog (Varian Associates, Palo Alto, California 1962) vol. 1, No. 51.
The MS of this fraction also showed significant peaks atm/e 135 (40%) and 195 (20%), the former associated with (6) and (8) arising by cleavage of the 8,10-bond, and the latter is associated with (7) and (9) originating by cleavage of the same 8,10-bond.
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Acknowledgements. We are indebted to ProfessorR. H. Thomson (University of Aberdeen, Scotland) for his interest and advice on this problem. We also wish to thank ProfessorE. Lederer and Dr.B. C. Das (Gif-sur-Yvette, France) for some mass spectra. The technical assistance of Mr.C. Di Pinto (NMR) andG. Scognamiglio is also acknowledged.
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Cimino, G., de Stefano, S. & Minale, L. Oxidized furanoterpenes from the SpongeSpongia officinalis. Experientia 30, 18–20 (1974). https://doi.org/10.1007/BF01921570
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DOI: https://doi.org/10.1007/BF01921570