Neolignans fromAniba ferrea

Neolignans fromAniba ferrea

Phytochemistry, Vol. 31, No. 1, pp. 271-273, Printed in Great Britain. 0031-9422/92 1992 (c? NEOLIGNANS $S.OO+OO 1991Pergamon Press pk. FROM ANI...

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Phytochemistry, Vol. 31, No. 1, pp. 271-273, Printed in Great Britain.

0031-9422/92

1992 (c?

NEOLIGNANS

$S.OO+OO

1991Pergamon Press pk.

FROM ANIBA FERREA*

DIONEIA C. RODRIGUES, MASSAYOSHI YOSHIDA and OTTO R. GOTTLIEB Instituto de Quimica, Universidade de Sio Paulo, 05508 Sio Paulo, SP, Brazil (Received 8 April 1991) Key Word Index-hibaferreq

Lauraceae; wood, benzylbenzoates; neolignans; ferrearins.

Abstract-The presence of benzyl benzoates as well as of bicyclo[3.2.l]octanoid and hydrobenzofuranoid neolignans in An&a ferrea was confirmed by the isolation of additional representatives of this class of natural products. The hydrobenzofuranoids included three novel ferrearins which, considered together with four known ferrearins, led to the stereochemical clarification of the group.

INTRODUCTION of Aniba ferrea (Lauraceae) [2] has been reported to contain benzylbenzoates (la-c) and dillapiol (2), as well as ferrearin- (&I, b), porosin- (4a, b), canellin(Sa) and guianin- (6) type neolignans. The compound numbers of the previous paper [3] are retained. However, the structural formulas, whenever necessary, are drawn in conformity with the chiroptic analyses performed during the present reinvestigation of the same species. This resulted in the additional isolation of the benzyl benzoate Id and of three new (3c-e) and three known (4c [4], 5b [S], 7 [6]) neolignans. The latter were identified by direct comparison with authentic samples. The heartwood

RESULTS The molecular formulae for 3c (C19HZ204), 3d (CzoHzz05) and 3e (Ci9HZ204), determined by low resolution mass spectrometry in combination with hydrogen and carbon counts by NMR, were expanded to Gu.Cr,H,,O,, Mp.C,,H,,OJ and Gu.C12H,,03, respectively, by routine inspection of ‘HNMR spectra (Gu . . . guaiacyl, Mp . . . 3-methoxy-4,5-methylenedioxyphenyl). The compounds thus should belong to the ferrearin type already known to be represented in A. ferrea by 3a (Mp.C,,H,,O,) and 3b (Pi.C,,H,,O,) (Pi . . . piperonyl) [3], in Ocotea aci-

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phylla by 3b and f (Pi. C12Hr503) [7] and in 0. catharinensis by 3f and g (Ve. C12H150J) (Ve . . . veratryl) [l].

OMe

The existence of guaiacyl substituents in 3c and e was confirmed by their ‘H and “CNMR spectral comparison with derivatives obtained by reaction with acetic anhydride and pyridine (room temp, 24 hr). The acetate

*Part 95 in the series ‘The Chemistry of Brazilian Lauraceae’. For Part 94 see Ref. [l]. Based on the doctorate thesis submitted by D.C.R. to Universidade de Slo Paulo (1990). 271

Neolignans from Anibaferrea 3.89 (s, OMe). “CNMR (50 MHz, CDCl,) 6: 135.76 (C-l), 101.41(C-2), 148.80 (C-3), 135.76(C-4), 143.37 (C-S), 106.96(C-6), 88.74 (C-7), 50.40 (C-8), 8.45 (C-9), 53.44 (C-l’), 100.02 (C-2’), 192.68 (C-3’), 125.27 (C-4’), 151.36 (C-S), 29.64 (C-6’), 39.52 (C-7’), 134.01 (C-8’), 117.69 (C-9’), 101.41 (O&H,), 56.57 (OMe). EIMS 70 eV (rel. int.) m/z: 358 ([Ml’, 25), 330 (M-CO, 18), 192 ([Mp.CHCHMe]+, 42), 179 ([Mp.CO)+, 32), 165 ([OMe.O,CH, tropylium]+, 43), 151 (ll), 91 (16), 79 (29), 77 (31). C~lss9 - 150.1” (1.82 mgml-’ MeOH). reI-(7R,8R,1’S,2’R)-4,2’-Dihydroxy-3-merhoxy-~-oxo-A~,8’8.1’,7.0.2’-neolignan (ferrearin H, 3e). Amorphous solid. IR vz:y cm-‘: 3464,1681,1636,1608,1514,1460,1437, 1384,1273, 1237,1191,1116,1098,1034. ‘H NMR (200 MHz, CDCl,) 6: 6.82 (brs, H-2, H-5, H-6), 4.63 (d, J=9.8 Hz, H-7), 2.46 (dq, J=6.7, lO.OHz, H-8), 0.95 (4 J=6.8 Hz, H,-9), 6.13 (ddd, J=O.9, 3.1, 10.2 Hz, H-4’), 6.99 (ddd, J=2.6, 5.8, 10.2 Hz, H-5’). 2.28 (dd, J =5.8,20.0 Hz, H-6’,,), 2.64 (dt, J=2.8, 20.0 Hz, H-6’,,), 2.50 (dd, J=6.7, 13.2 Hz, H-7’A), 2.13 (dd, J=8.2, 13.6Hz, H-7’B), 5.60 (dddd, J=6.8, 8.3, 9.9, 16.8 Hz, H-8’), 5.03 (dm, J= 16.8 Hz, H9’E), 4.93 (dm, J=9.9Hz, H-9’Z), 3.90 (s, OMe). ‘%NMR (20 MHz, CDCI,) 6: 132.88 (C-l), 109.59 (C-2), 146.83 (C-3), 145.49 (C-4), 113.82 (C-5), 120.49 (C-6). 88.80 (C-7), 50.27 (C-8), 9.36 (C-9), 53.43 (C-l’), 99.98 (C-2’), 192.85 (C-3’), 125.20 (C-4’), 151.44 (C-5’),29.60 (C-6’), 39SO(C-7’), 134.06(C-8’), 117.60 (C-9’), 55.84 (OMe). EIMS 70 eV (rel. mt.) m/z: 330 ([Ml’. 19), 302 ([M

273

- CO]+, 14), 164([Gu.CHCHMe]+, 70), 151 ([Gu.CO]+, 44), 137 ([OH. OMe. tropylium] ‘, lOO),123 (22), 109 (39), 107 (24), 93 (3% 81 (39), 79 (43). Calm - 78.4” (2.26 mg ml - 1 MeOH). Acknowledgement-The authors FAPESP for financial support.

wish to thank CNPq

and

REFERENCES

1. Ishige, M., Motidome, M., Yoshida, M. and Gottlieb, 0. R. (1991) Phytochemistry 30,412l. 2. Kubitzki, K. and Renner, S. (1982) Flora Neotropica (The New York Botanical Garden), Monograph 31,80. 3. Andrade, C. H. S., Braz-Filho, R. and Gottlieb, 0. R. (1980) Phytochemistry 19, 1191. 4. Cavaleante, S. de H., Giesbrecht, A. M., Gottlieb, 0. R., Mourlo, J. C. and Yoshida, M. (1978) Phytochemistry 17,983. 5. Giesbrecht, A. M., Franea, N. C. and Gottlieb, 0. R. (1974) Phytochemisrry 13,228s.

6. Lima, 0. A., Gottlieb, 0. R. and Magalhles, M. T. (1972) Phytochemistry 11,2031. 7. Romoff, P., Yoshida, M. and Gottlieb, 0. R. (1984) Phytochemistry 23, 2101. 8. Felicio, J. D’A., Motidome, M., Yoshida, M. and Gottlieb, 0. R. (1986) Pkytochemistry 25, 1707.