ESSESTIAL OILS FROM BRAZILIAN T7ERBENACEAE. GEKUS LIPPIA A . .A. Clt4\EIRO, J. \$'. .4LEXL4R, F. J . .A.
;\14TOS,
c. H. S . ANDRADE and AI. I . L. MACHADO
~ n z v e r s z d a d eFederiil do Ceiird, Deparlnnienfo de Qztinizcn Orgdnzca e Inorg&nzca, Centro de Cze'ncziis, C ~ I Z LPOSfUl ~ L 955, 60.000, Forfaleza, Ceard, Brazzl .ABSTR.4CT.-EsseIltial oils from six species of t h e 1.erbenaceae family; L z p p i a alba, L . nlnifolici, L . u f l n i s nristeifn, L . uristain, L . grato and L . n j . sidoides were analyzed by gc-ms-computer library search programs. Several monoterpenes, sesquiterpenes, aromatic compounds, alcohols, and ketones were identified. Thymol and a-phellandrene are the major constituents of t h e essential oil of L . off. sidoides. T h e other five species contain mainly caryophyllene follom-ed by carvacrol in L . u172ifo/i(i and L . grato, y-cadinene in L . ( i f f . u r i s f n f a , sabinene in L . uristafa, and geranial in L.cilbii.
File.
Species
L . a.?. orislato Schau. L . arislata Schau.
F-518 F-517 F-101
1
,
Collection Bites (Brazil)
'1
Pb.f
'
L . a.f. sidoides Cham. I
When collected
Part studied
~
,-ieldc
~
Gept. i S Xo\- 77
leaves leaves
0 4
A u g . ii
leaves
4 0
15
Craveiro et al.: Essential Oils of Lippia
Jul-Aug 19811
599
tographic (gc) retention indexes. These programs were written in BASIC language and implemented in our laboratory for automatic analysis of essential oils (21-22). Confirmations of the identifications were carried out by visual comparison of the full ms with standards from a certified collection ( 2 3 ) ,by other spectrometric TABLE 2. Chemical composition of essential oils of 1-erbenaceae species, genus Lzppia. Constituent
L.ulba L alni- 1 L.01. L.u n s -
~
folza
I
camphene car-3-ene limonene m) rcene a-phellandrene a-pinene y-t erpinene sabinene a-t hujene
. . . . . i
-
. . . .
0.8
i
. I
2.5
. . . . . . . . . .I
1.2
-
I
. . . . . .
camphor 18,cineol geranial linalool neral terpinen-4-01
1.3 6.3 1.o 1.2 1.2 11 .o 1.2
-
. . . . . . . . . .
-
I
l
uristafa 1
-
I
Confirmation
-
1.9 16.8 -
1.4
22 4 0 6 4 3 2 0
-
21.1 1.1
1
a, b, c a,b a,b -
-
alloaromadendrene y-cadinene 6-cadinene @-car>ciph! llene a-copaene 8-elemene -,-elemene a-muurolene -,-muurolene a-humulene
I
_-__ -
-
-
1
07 24 1243 18 1 1 5 I
I -
0 4
______~___
1
2 2
37.4 -
32.5
-
0.8 12.4 -
2 1
-_
- -1 - -1
caryophyllene oxide?
1
i ~~
Total*
L. aJ. sidoides
129 9 6
carvacrol. . . . . . . . . carvacrol acetate. . , . . I eugenol . . . . . . . . . . . . i 0-methyl-thymol.. . . . . . . t h y m o l . .. . . . . . . . . I thymol acetate . . .I
2-undecanone
~
grata
-
'
___ __-____
~
L.
tufa
-
-
. . . . . . . . . . . . . . . . . . . . . . . . . . . 9 0
-
-
70 1
93 3
96 9
I
-
891
1 - 1
~
-
1 9 5 7 ' l
a . Kovat s indeues:.b. nmr: c . ir. 'Summation o f the c,r amount of each compound identified in the oil.
821
I -
-I -
GOO
,Journal of Satural Products
[Vol. 44, s o . 5
data and by comparison with authentic samples Ivhen they were available (see table 2). Lippia aJ. aristata (table 1) has some minor morphological differences as compared with the description of L. aris~atain the literat'ure (24). E'rom table 2, it is seen that essential oils of both species have the same major constituents, i e . , P-caryophyllene, y-elemene, and limonene; a-phellandrene (1.O%) was found only in Lippia aristata, u-hereas p-cymene (1.6%) n-as identified only in L. aff. aristata (see table 2 ) . Data from table 2 show that the essential oil of Lippia alba from Brazil is largely composed of P-caryophyllene (24.3YG) geranial (12.9Yc), neral (9.6y0), and 2-undecanone (9%,). These results do not agree with the chemical composition of the essential oil from the same species from Argentina which chiefly consist of dipentenes, d-limonene, and 1-piperitone (19).
EXPEKIAIESTAL T h e plant materials were collected a t locations mentioned in table 1 . Botanical identifications were made by A. G. Fernandes and P . Bezerra. A voucher of each species, under the number specified in table 1, is kept in t h e herbarium of Departamento de Biologia d a Universidade Federal do Ceara, Brazil. Essential oil extraction (25) was carried out by steam distillation of finely ground material for approximately one hour. T h e yields are reported in table 1 . T h e fresh oils were analyzed in a Finnigan 3300 quadrupole mass spectrometer coupled to gas chromatography with an open tubular glass column (30m x 0.25mm). S P . 2100 (methglsilicone) was used a s t h e stationary phase. T h e gc experiments were carried out under programmed temperature conditions (50°-2500) a t a r a t e of 4"/min with helium a s carrier gas. T h e ms fragmentations were carried out a t 70 eJ. electron impact. Mass chromatographic retention d a t a were calculated a s K o v a t ' s indexes (26) by co-injection of the essential oil with eight standard n-hydrocarbons (Cg, Cg, Cia! C11! C12, (214, ( 3 1 6 , and CIS). T h e reconstruction of t h e individual chromatograms of essential oil and n-hydrocarbons were carried out with ions m / z 91 and m / z 85, respectively (22). All d a t a processing was performed on a 6115 Finnigan computer with 32K bites of core memory equipped with a 3 megabite disk and with magnetic tapes. Other spectrometric d a t a (nmr, ir) were obtained with t h e aid of Varian Ehl 360, Varian XL-100 nmr instruments and a Perkin Elmer 720 infrared spectrophotometer. rlCKYOWLEDGMENTS T h e authors thank Conselho Nacional do Desenvolvimento Cientifico e Tecnol6gico ( C N P q ) , Banco do Kordeste do Brazil ( B N B ) and Financiadora de E s t u d o s e Projetos ( F I N E P ) for financial support. LITERrlTURE CITED 1 . I. 1.. Rovest, .Inn. Chim. Applicata, 17, 553 (1972); Chem. Abstr., 22, 1434 (1928). 2. E. H. Ducloux and C. Albizzatti, Rer. Fac. Cienc. Quim. Cniv. L e Plata (1927), Chem. Absfr., 22, 3951 (1928). 3. L. Pereyra, 17nir(.,Vocl. Tucumun Milrseo Historia Natural, 8, 3 (1926), Chem. Abstr., 22, 138 (1928). 4. J. Rabat6, Rer'. Bot. Appl. Agr. Trop., 18, 350 (1938) in Chem. Abstr., 32, 8701 (1938). 5. J. RabatC, J . Pharm. Chim., 28, 437 (1938), Chem. Abstr., 33, 8920 (1939). 6. X . G. Arrilaga, Puerfo Rico Agr. Erpt. Sta., Ann. Rept., 1939, 28 (1940), Chem. Abstr., 36, 5614 (1942). 7. %. G.'Arrilaga, A m . Perjumer, 45, 27 (1943); Chem. Abstr., 37, 1225 (1943). 8 . G. A. Fester, Ciencia e Invest. (Buenos Aires), 3, 327 (1947), Chem. Abstr., 41, 7056 (1947). 9 . G . A. Fester, hl. A. Gargalho and E. A. Blartinuzei, Annales Soc. Cient. Argentina, 144, 457 (1947), Chem. Abstr., 42, 4309 (1948). 10. D. J. Cosgrove, T . Slip and F. hlajor, Colonial Plant and Animal Products (Brit), 1, 56 (1950, Chem. Abstr., 44, 11033 (1950). 11. G. A. Fester and E. A. hlartinuzzi, Rev. Fac. Quim. Ind. e Agric. (Univ. Nacl. Litoral Santa FC, Arg.), 19, 54 (1950), Chem. Abslr., 45, 7306 (1951). 12. H. T. Slip and W. S.A. hlatthews, Colonial Plunt and Animal Products (London), 2, 96 (1951), Chem. Abstr., 48, 6073 (1954). 13. G. A. Fester, E . A. Martinuzzi and A. I. Ricciardi, Rev. Fac. Ing. Quim. (Santa FB, Arg.), 20, 47 (1951); Chem. Abstr., 48, 6655 (1954). 14. .J. F. Canosa, Ree. Asc. Bioquim. Argentina, 18, 225 (1953), Chem. Abstr., 48, 3638 (1954).
Sep-Oct 19811
Craveiro et al.: Essential Oils of Lippia
601
15. L. Palfray, S.Sabetay and P . P e t i t , Chimie 3 Industrie, 43, (1940), Chem.
