Chemical Studies of Myristicaceae Species of the Colombian Amazon

Chapter 11

Chemical Studies of Myristicaceae Species of the Colombian Amazon Juan C. Martinez V. and Luis E. Cuca S.

Downloaded by FUDAN UNIV on December 23, 2016 | http://pubs.acs.org Publication Date: March 31, 1995 | doi: 10.1021/bk-1995-0588.ch011

Departmento de Quimica, Universidad Nacional de Colombia, A.A. 14490, Santafé de Bogotá, Colombia

Amazonian societies of Brazil and Colombia make ample use of species belonging to the Myristicaceae family as medicines, hallucinogens and arrow poisons. Analysis of seven such species affored a large number of novel compounds, chiefly neolignans (coupling products of propenylphenols and allylphenols) and iryantherins (coupling products of dehydrochalcones and neolignans). Since early times, plants have been used by man to cure his diseases. Our natives and Indians knew and manipulated, with surprising effectiveness, the healing powers of plants. This healing power, without doubt, is due to the substances that the plant produces during its development, as a result of its metabolism. Colombia is a fortunate country in terms of its rich variety of plants, most of which are found in the Amazon Region; but, unfortunately, some species have disappeared and others will follow the same path, in the name of progress, due to the indiscriminate felling of our primary forests, wich will keep us from knowing the metabolites of these species. Besides, the effects of erosion and soil degradation will convert our jungles into deserts. Our phytochemical research group has centered its interests on studies of the Myristicaceae. Papers that raised most interest in the study of plants of this family were published by Schultes (7-3) and Gottlieb (4). Table I, adapted from the literature (4), gives an idea of the use of Myristicaceae by Amazon Indians. The contents of the Table provide a serious motivation for the necessity of submitting species of this family to phytochemical and pharmacological studies. The Myristicaceae family belongs to the order Laurales and includes 19 genera (Table II), six of which are native to the American Continent. According to the vouchers that are kept in the Colombian National Herbarium, 50 species of these seven genera have been collected in our country, as shown in Table ΙΠ.

0097-6156y95y0588-0116$12.00A) © 1995 American Chemical Society Seidl et al.; Chemistry of the Amazon ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

11. MARTINEZ V. & CUCA S.

Myristicaceae Species of Colombian Amazon

Table L Uses of Myristicaceae by Indians of the Amazon


Genera

Plant part Preparations Uses or treatments

Compsoneura leaves bark Diafyanthera seeds

tea decoction butter

Iryanthera

leaves

plaster

bark latex fruit leaves bark

decoction

Virola

seeds

tea decoction decoction with ashes butter

kino sap AdaptedfromGottlieb, ref. (4).

mental disorder, trembling infected wounds, ulcers skin infections of domestic animals,erysipelas, hemorrhoids infected wounds, infections by fungi, itching of skin infections by fungi, erysipelas stomach poisoning fish bait tea substitute vitiligo, tooth ache hallucinogenic powder and tablets, arrow poison rheumatism, intestinal worms, asthma, bad breath colics, bleeding, ulcerated wounds hemorrhoids

Table Π. Genera of the Myristicaceae family Brochoneura Haematodendron Horsfieldia Cephalosphaera Coelocaryon Iryanthera* Compsoneura* Knema Maloutchia Diafyanthera* Myristica Endocomia Gymnacranthera * Genera native of the American continent.

Osteophloeum* Otoba* Pycnanthus Scyphocephalium Staudtia Virola*

Seidl et al.; Chemistry of the Amazon ACS Symposium Series; American Chemical Society: Washington, DC, 1995.

117

118

CHEMISTRY OF THE AMAZON

Table HI. Species of Myristicaceae found in Colombia


Genera Compsoneura Diafyanthera Iryanthera

Number of species Genera 5 Osteophloeum 5 Otoba 11 Virola

Number of species 2 3 24

Our investigations on species of this family have, as a first, short term objective, the isolation, purification and identification of secondary metabolites of different parts of the plant. We studied ten species (Virola calophylla, V. calophylloiaea, V. carinata, V elongata, V sebifera, Iryanthera Iaevis, I. pavonis, I. tricornis, Compsoneura atopa and Osteophloeum sulcatum). Some of the results of these studies are given below. Virola calophylla From bark (5) and leaves (6) lignans of several types were isolated and identified. The former was shown to contain four neolignans of the dibenzylbutane type la, lb, 2a and 2b, one of the benzoylbenzylbutane type 3a, two aryltetralins 4a, 4b, and three of the arylnaphthalones 5, 6a and 6b. In the latter three neolignans of the dibenzyl type la, lc and 2a, and one neolignan of the tetrahydrofurane type 7 were identified. Virola calophylloiaea Benzene extracts of leaves, bark and wood were examined. Metabolites identified were of the neolignan,flavonoidand steroid type. The leaves possess a steroidal fraction. GC, HPLC and GC-MS studies indicated that it was composed of a mixture of colesterol, sitosterol, stigmasterol and three other unidentified sterols (7). Four neolignans 8, 9, 10 and 2c were also isolated in pure form (8,9). It was shown that compound 10 is produced by dehydration of 9 in acid medium. The substances 8, 9 and 10 were also identified in bark. Wood afforded three flavonoids (10), a flavone 11, an a-hydroxydehydrochalcone 12, and a 1,3diarylpropane 13a, as well as an alkaloid, 3-indolcarboxaldehyde (77). Virola carinata Wood of this species was studied in Brazil and bark in Japan. From the benzene extract of the leaves (72) we isolatedfivecompounds 14,15a, 15b, 15c and 16, all of the lignoid type. Substances 15a, 15b, 15c and 16 are part of an exceptional series of compounds which we called pseudoneolignans, since the sole oxygenation of C-9 and lack of oxygenation at C-9' does not allow us to include them either




l

!

la Ar=Gu, Ar =Pi lb Ar=Ve, Ar^Pi lc Ar=Ar Gu

1=

1=

3a Ar=Gu, A r P i 3b Ar=Pi, A r ^ V e


1=

2a Ar=Gu, Ar =Pi 2b Ar=Ve, Ar*=Pi 2c A r * A r G u


119

120


among the lignans or the neolignans, the former with oxygenation at both positions and the latter without oxygenation at either position, as defined by Gottlieb (13). Viroia elongata Three neolignans were isolated and identifiedfromthe benzene extract of the bark of this species (14). Two, 17 and 18, correspond to the tetralone type and the other, 3b, to the benzoylbenzylbutane type.


Viroia sebifera V sebifera is the most widely studied species of the Myristicaceae family. The fruit was studied in Brazil and a large number of metabolites (15-19) which correspond to four polyketides, six lignans and 19 neolignans were identified. The bark was studied inVenezuela (20) and Japan (27, 22), fatty acid derivatives, six alkaloids, one terpene and two lignans having been identified. Leaves, bark and wood were studied by our group. Three fiirofuran lignans, (+)-sesamine 19a, (+)-kobusine 19b, and (+)-eudesmine 19c, were identified in the leaves (23). Two lignans, (+)sesamine and (+)-kobusine, were identified in the bark (24) and three 1,3diarylpropanes, 13b, virolanol Β 13c, and virolanol C 13d were found in the wood (77). Iryanthera laevis We studiedfruitand bark of this species which is known by several common names such as "otoba or "kimo" in Caqueta, and "mamita in Meta (region of San Martin). The inhabitants of this last region eat the aryl of the fruit as a sugary preparation. Fruits were separated into mesocarp, aryl and kernel and each of the parts was studied sparately (9, 25) revealing dihydrochalcone type compounds in all of them. Compound 20a was isolated from the three parts of the fruit, compounds 20b, 21 and 22a were obtainedfromthe aryl, compounds 21, 22a and 22b from the mesocarp and compound 23 was obtained from the kernel. Four dihydrochalcones, 20a, 20c, 20d and 24 were identified in the bark (26,27). In the iryantherins 21, 22a, 22b, 23 and 24 the dihydrochalcone unit bears a lignoid substituent. M

M

Iryanthera tricornis Dihydrochalcones 20a and 24 were found in the bark while 1,3-diarylpropanes 13e, 13f and 13g were isolatedfromthe wood (28).



Myristicaceae Species of Colombian Amazon 121

OR !

2

R

~ R

OR

4

3

3

13» R=H, R -R =Me, R*=R =R -H 2

J

13b R - H , R - R ^ R ^ H , R =R =Me 4

13c R=OH, R ' ^ R ' - R ^ H , R =MC 1=

OH

Ο

4

2

S

5

13d R=OH, R R =Me, R =R =R =H


13e R=H, R ^ R ' - R ^ H R ^ R ^ M C !

2

!

2

S

13f R=H, R =R =R -H, R ' + R ^ - C H J 3

4

3

13g R=H, R = R - H , R +R =-CH,-, R =OMe

l

2

!

2

3

4

19b R=R =Me,R +R =-CH23

4

19c R=R=R=R=Me




122


11.

ΜΑΚΉΝΕΖ V. & CUCA S.


Literature cited 1. 2. 3. 4. 5. 6.


7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28.

Schultes, R. E., Botanical Museum Leaflets, Harvard University 1954, 16, 241-260. Schultes, R. E., Botanical Museum Leaflets, Harvard University 1969, 22, 229-240. Schultes, R. E. and Holmstedt, B. Lloyadia 1971, 34, 61-78. Gottlieb, O. R. J. Ethnopharm. 1979, 1, 309-323. Martínez V., J. C.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1990, 29, 2655-2657. Alvarez, E.; Cuca, L. E.; Martinez V., J. C. Rev. Colombiana Quím. 1985, 14, 31. Cuca, L.E.; Martínez V., J. C. Rev. Colombiana Quím. 1984, 13, 109-118. Martínez V., J. C.; Cuca, L. E.; Yoshida, M . ; Gottlieb, O. R. Phytochemistry 1985, 24, 1867-1868. Garzón, L., Cuca; L. E., Martínez V., J. C.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1987, 26, 2835-2837. Martínez V., J.C.; Cuca, L.E. J. Nat. Prod. 1987, 50, 1045. von Rotz, R.; Cuca, L. E.; Martínez V., J. C. Rev. Colombiana Quím. 1990, 19, 97-100. Guarin, C.; Cuca, L. E.; Martínez V., J. C. Spectros. Int. J. 1988, 6, 107112. Gottlieb, Ο.R.Fortsch. Chem. Org. Naturst. 1978, 35, 1-71. Martinez V., J. C.; Cuca, L. E.; Santana, R.; Pombo-Villar, E.; Golding, B. Phytochemistry 1985, 24, 1612-1614. Lopes, L. M . X.; Yoshida, M.; Gottlieb, Ο. R. Phytochemistry 1982, 21, 751-755. Lopes, L. M . X.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1983, 22, 1516-1518. Lopes, L. M . X.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1984, 23, 2021-2024. Lopes, L. M . X.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1984, 23, 2647-2652. Kato, M. J.; Lopes, L. M . X.; Paulino Filho, H. F.; Yoshida, M.; Gottlieb, O. R. Phytochemistry 1985, 24, 533-536. Corothie, E.;. Nakano, T. Planta Medica 1969, 17, 184-188. Kawanishi, K.; Uhara, Y.; Hashimoto, Y. Phytochemistry 1985, 24, 17731775. Kawanishi, K.; Hashimoto, Y. Phytochemistry 1987, 26, 749-752. von Rotz, R.; Cuca, L. E.; Martínez V., J. C. Rev. Colombiana Quím. 1987, 16, 51-55. Martínez V., J. C.; Cuca, L. E.; Martínez, P. Rev. Colombiana Quím. 1985, 14, 117-125. Conserva, L. M.; Yoshida, M.; Gottlieb, O. R.; Martínez V., J. C.; Gottlieb, H. E. Phytochemistry 1990, 29, 3911-3918. Villamil, E.; Cuca, L. E.; Martínez V., J. C. Spectros. Int. J. 1988, 6, 157165. Martinez V., J. C.; Cuca, L. E. Rev. Colombiana Quím. 1989, 18, 37-46. Salazar, L. M.; Cuca, L. E.; Martínez V., J. C. Rev. Colombiana Quím. 1988, 17, 33-37.

RECEIVED December 16, 1994


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Chemical Studies of Myristicaceae Species of the Colombian Amazon

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