CORIAMYRTIK A N D OTHER METABOLITES OF CORIARIA RUSCIFOLIA A . REYESQ.,R.M A R T ~ S JE. Z Iizstitziio d e Qitimica, Gwi-jersidad Aztsiral d e Cliile, Valdizia, C h i l e and
J. BARTUL~S Iiistitzito C e n t r a l d e
Qzlii7iica1
I;izii.ersidad d e C o i i c e p c i d u , C h i l e
Coriamyrtm iq a picrotoxinoid lactone isolated from Coriaria j a p 6 u i c a (1) and C . myrtijolia ( 2 ) . O h d a and Yoshida proposed a structure and absolute configuration for it by analogy n-it11 picrotoxin (3). The chemical >tudy of S e n Zealand C. ruscif o l i a L. led Easterfield and Aston ( 2 ) to isolate tutin, another picrotoxinoid sesquiterpene lactone. Hon-ever in the case of C.ruscijolia L.. the oil11 representative in Chile of the family Coriaceae (4), coriamyrtin TT a > isolated inatead of tutin. The structure of coriamyrtin ]vas determined as structure 1 by spectroscopic methods : ir, 'H-nnir, I3Cnmr ( 5 ) and nit. I n addition, the compounds @-sitosterol and ursolic acid were isolated. The ir spectra of these cornpounds n ere superimposable n ith authentic samples' of @-sitosterol and ursolic acid, and the mixture melting points u-ere undepressed. Furthermore, the follon-ing phenolic compounds u-ere iaolated: quercetin, quercetin-3-0-galactoside, avicularin and quercitrin. They 13-ere identified on the basis of their physical properties as compared 11-ith authentic samples' (Rf, mixture melting point) and by direct coinparison of their 1 . i ~ spectral data viith those found in the literature (G). EXPERII\IESTAL Voucher specimens are deposited in t h e Herbarium of t h e Botany Institute of t h e 'These authentic samples -are kindly donated b y D r . 11.Silva of t h e Cniversity of Concepci6n. 532
Universidad Llustral of Chile (Herbarium S o . 3810-3800). T h e aerial p a r t of a dried ground plant (T200 g ) , collected in Pishuinco, Province of Taldivia in January of 19T7, v,-as exhaustively extracted n-ith 95% ethanol after prior treatment with benzene t o remove t h e lipid fraction. T h e ethanol extract vias concentrated in i'ocuo and diluted with distilled m-ater, v h i c h q-as successively extracted with benzene, chloroform, e t h y l acetate and amyl alcohol; thereby 30 g of benzene extract, 15 g of chloroform extract, 112 g of ethj-l acetate extract, and 1 2 i g of amyl alcohol extract n-ere obtained.
1-Coriamyrtin TOSTE STEROL . ~ S DURSOLIC .icIo.-The benzene extract was chromatographed over silica gel (Merck) and eluted with solvents and solvent mixtures of increasing polarity beginning with petroleum e t h e r (G0-8OCC). A white crystalline povider p-as obtained from t h e fraction eluted v-ith benzene. I t n-as crystallized from ethanol (1.50 g, mp 138°C). T h e m p and mmp determination m-ith an authentic sample of B-sitosterol indicated the identity of this compound t o he B-sitosterol. T h e i r (Xujol) gave 3000, 3200, 1040, and i o 0 em-'. By means of t h e usual methods of acetylation, t h e acetate of B-sitosterol (mp 12G'C) n a s obtained; i t gave bands (Nujolj a t 1740, 1250, and 1080 cm-1. F r o m t h e fraction eluted R-ith ben-
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REYES (I. ET AL.:
zene-methanol (7:3) --as obtained a white solid which crystallized from ethanol (2.5 g, m p 278-BOT); i r (Sujol):,360CL3300, 1700, and 700 cm-1. T h e identity of this compound was verified as ursolic acid b y no depression in mixture mp with an authentic sample. T h e acetate of this white solid h a d a m p of 289-290°C: it gave i r bands 1Sujol) a t 3200, 1T10, 1250, 1050 em-'. CORIIMTRTIS (1).-The chloroform est r a c t was chromatographed over 100 g of silica gel n-ith solvents and solvent mixtures of increasing polaritj-. T h e fraction eluted b y chloroform-methanol i l : l ) yielded a n-hite solid n-hich, after successive recrystal1izatio:is from methanol yielded, 3 g of a crystalline product, nip 228'C: Fif 0.13 ichloroft3rm silica gel); i r ( S u j o l ) 3600-3200 (OH), 1770, li60 (lactone), 1650 ( C = C ) , and llG0 em-' (epoxide). QUERCETIS. I S D QUTERCETIS-3-O-~.IL.~CTOsIDE.-From t h e e t h y l acetate fraction, which was chromatographed over a cellulose column and l a t e r over polyamide, n-as isol a t e d 1.5 g ofquercetin and 1.2 g ofquercetin3-0-galactoside. h T I C T L . i R I S . 1 S D QUERCITRIS.-The amj-lic fraction, n-hen chromatographed in a manner similar t o t h a t of t h e anterior fraction, yielded two flavonoids which, upon comparison with authentic samples', n-ere identified as avicularin 10.50 g ) and quercitrin (0.80 g ) .
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EXTRACTIOS OF THE FRrITs.-The fruit of C. ritscifoiia L. (500 g) was exhaustively extracted with refluxing methanol. T h e methanol extract was chromatographed over silica gel x-ith appropriate eluents; this permitted t h e isolation of t h e compounds $-sitosterol, ursolic acid and coriamj-rtin. hCHSOWLEDG?rlESTS We are grateful t o t h e D i r e c c i h de Inv e s t i g a c i h Cientifica d e la Vniversidad Austral de Chile (Grant RS-ii-49) for support of this nork. The authors also n-ish t o thank Dr. Mario Silva of t h e Vniversidad d e Concepcibn, Chile, for permitting t h e use of his iiv spectrophotometer. LITER-ITCRE CITED 1. T . Kariyone and T . Sato, J . Phartn. S O L . Jaball. 50. 106 119301. 2 . T.'H.'Easterfield and B. C. Aston, -7. C h e m . S O C . , 120 (19011. 3. T . Okuda and T. Toshida. T e i r a h e d r o n L e f i e r s , 439, e r r a t a 694 (1961). 4. C . Munoz P., "Sinopsis de la flora chilena" Ediciones de la Universidad d e Chile , p. 118, 11959). 5 . G. C. Lev>-, G . L. Selson, Carbon13 S u c l e a r Magnetic Resonance for Organic Chemists , John R i l e y & Sons, Inc. U.S.A., p . 59 and 119, (1972). 6. T. J. X a b r y , K. R.M a r k h a m and 11.B. Thomas, "The Systematic identification of Flavonoids", Springer-T-erlag, S e n - Torli-Heidelberg-Berlin, p. 126, 128 and 129, 119iO).
