FIXED *AND T'OLATILE CONSTITUENTS O F C R O T O S A F F . ,YEPETIFOLIUS' 1.-1 CRIIEIRO,C. H. S.AXDRLDE, F .J A4 XATOS, J \I' A L E ~ C Land R T N . C. D \ \ T \ s Ctiiaersidade Federal d o Ceard, Departamento de Q2iinzzca Orgciwca e Izorgcinzca, Cenfro de Ci&ncias,Cairn Postal 935 60.000 Forlera - Ceard - B r a d
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Crotoiz u j . wpetijoliui. Bail iq a small tree of the Euphorbiaceae family \videspread in the Brazilian northeast. The plant reaches a height of 4-6 m. I t is commonly laown as Alarmeleiro SabiA and is used in folk medicine for gastric diseaqe treatment. The preqent chemical study was conducted as part of a general screening program of Brazilian essential oil producing plants having pharmacological activity.
DISCUSSION
ptene, a-cubebene, 6-elemene, a-santalene, and n-propyl catechol are being reported for the first time as volatile constituents in this genus.
EXPERIAIESTXL Taxonomic identification was made by G. L. Webster, University of California, Davis, and A. G . Fernandes, Universidade Federal do CearL, Brazil. A voucher specimen is deposited in the herbarium of the Departamento de Biologia, Universidade Federal d o Cearh, under number 3185. The plant n-as separated into leaves, stems, hark, and wood and then finely ground before extraction.
The specimen was collected in ISOL.ATIOK or COSSTITUESTS.-U) A benzene Sobral, State of CearA, on 1Iarch extract of the wood submitted t o chromatographic filtration on silica yielded 197'7. Essential oils from stems, fractions n-hich m-ere eluted with hexane, leave.. bark, and wood Ti-ere obtained benzene and acetone. Silica chromatogby steam distillation. Volatile conraphy of the benzene eluate with chloroformmethanol mixtures as eluent, produced three stituents in each sample are described solids and two oily substances. The solids in table 1. Nonoterpenoids constiwere purified by crystallization from cyclohexane and the oils by preparative tlc. b ) tute the major part of the essential oil Essential oil extractions were carried out bjfrom lesser lignified tissues (leaves and steam distillation of each part in an appabark), n hereas seqquiterpenoids and ratus developed in our laboratory ( G ) . Yields are reported in table 1. Each espropenylbenzene derivatires are the sential oil, after separation, was dried v5th major products in the oil of lignified anhydrous sodium sulfate, filtered, and sealed in glass vials under nitrogen atmotissues (stemi: and nood). sphere. The oils n-ere submitted t o g v m s Chromatography of the benzene esseparation on a Finnigan 3300 quadrupole mass spectrometer coupled t o a gc equipped tract of the wood yielded isolation of with capillary glass column (0.25 m m x 30 m ) five pure known substance., namely, coated with SP 2100 (methyl silicone) with ~ - h ~ - d r o x y - ~ , ~ . 6 - t r i m e t l i o s ~ - a c e t o p l ihelium eas the carrier gas and ms spectra nolie (1), 2-li\-droxy-~.G-di;e~l~oxy- recorded at i o ev. Substances isolated from the benzene exacetophenone (xanthoxylin) (2), 1, tract were identified by spectrometric an2-diniet hoxy-5- (2-propenyl)-benzene alysis (ir, nmr and ms) and derivative preparation. Xanthoxylin identification was (met!:;\ 1 eugenol) (3). 1.2.3-trimethox~confirmed by comparison of the mixture nip 5- (2-propen!-l)-benzene (elemicinj cnci n-ith t h a t of an authentic sample. ~?-OCtaCOSaliOl(4). Only eleiniciii and Constituents of essential oils n-ere identified chiefly hy tn-o ms library search prometliyl eugenol (3. 5 grams, BUSC 6 and modified Finnigan PF ported $0 far from extractivec of the ( i j , and h>- a 1ibrar:- search program , o r genu< C~oto71; whereas, a-bergamoauton:atic determination of Kovats ret.e!i'Extracted in part from the 11Sc Thesis of T. X . C . Dantas presented a t Cniversidade Federal do Cearg, 1979.
tion indexes. Results of the above computer programs 15-ere confirmed by ms visual analysis and lor comparison n-ith authentic samples (table 1 ) .
SOV-DEC
19801
C R A V E I R O ET AL.:
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C R O T O S AFF. SEPETIFOLICS
151
TIBLE1. Chemical compositlon of t h e essential oil of Croton a-ff. izepeizjolzlLs Bail. Part of plant and > ields of individual components ($
Constituent
MOSOTERPESOIDS camphene camphor l,&cineole a-pinene 3-pinene sabinene a-terpineol TOTAL SESQUITERPESOIDS a-bergamoptene' 6-cadinenec 3-caryophyllene a-copaene a-cubebene B-elemene" 7-elemene 6-elemene humulene a-santalene others sesquiterpenes
'
Leave.
Stems
Wood
Bark
_ _ _ - _ _ _ ---_
~-
I
l
ms, ri
37 5
3 0
1
-
I__-_
47;
ms, ri, a s ms, ri, as
1 5
1 5
1
1
-
~
-
1
-15 _-__ ~
-
1 ~
ms,ri -
-______
1
4 0 -
-
1
-
6 5
I
3 0
ms ms ms, ri, as
3 0
23 0 3i 5
-
1 0
120 4 5 2 0 l
-
I
-
-
'
6 5 ' 3 9 5
,
-
2 0
3 0
290
25 0
80 0
77 5
15.0
14.0 -
425
PHESTLPROP-4SOIDS . elemicin . . . . . . . . . . . . nieth>-l eugenol. . . . . . . . . . . . . . . . propyl c a t e c h o l . . . . . . . . . . . . . . . ..~
0.5 1.0
I
-
,
-
TOT.4L
5 0
1
1 0
1
150
j
32 5 1 0
-
,
TOTAL
1 Identification process'
I
I
960
1
140
ms nis, ri ms, as ms ms ~ _ -
I
i
_
-
ms, as nis, as ms -
3Percent yields of oil relative to d r y part of t h e plant x-ere: leaves (0.9%), stems (0.4$), bark (1.3c; I, wood (0.1%). b m s = l I a s s Spectrum: r i = K o v a t s Retention Index; as= authentic sample. Comparison with reference spectrum. S o authentic samples available. .1CKSOWLEDG;\IEST The allthors are grateful " t h e Conselho Sacional de Desenvolvimento Cientifico e Tecnol6gico ( C S P q I ; Banco do S o r d e s t e do B r a d S..k. I B S B ) and Financiadora de Estudos e Projetos S..1. IFISEP) for financia1 support and t o Prof. -4.B . Oliveira, Universidade Federal d e Minas c k r a i s , Brasil, for a generous gift of santhosj-lin. Received 2 Ma? 1980. LITERATURE CITED 1. S . N o r i t a , A I . Shimisu and A I . .Irisawa, Y n k i i p k i i Znsshz, 88, 1212-17 (1988).
2. S . Morita, 11..Irisawa and T. Taliayuki, 17ak71gnkit Zasslii, 87, 1017-19 (1907). 3, -4.-4,Craveiro, C , H . S.d n d r a d e , F. J. A. Alaros and J. R.Alencar, J . d g r i c . Food Cheii;., 26, 772 (1978). 4. A. ~ i ~ ~ T~~~ b ~de D ~ ~ h~ ~ niento ( P h D Thesis) r n i v e r s i d a d e de SBo Paiilo, S. Paulo, Brazil 11973). 5 , R,B~~~~~and ,J, crorrle5--, PhTiociienl~sfTy, 5 , 921-8 (1966). 6. A . Craveiro, .J. W .rilencar and F. J. A. l l a t o s . J . Ciieiii. Editc.. 33. 632
..
7
(1976). I ... T 7 =ILencar 41 and -4.-4.Craveiro, 178th
,.1
ACS S a t i o n a l Meeting, Washington, D C (1979).
September,
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