Composition of Aloysia gratissima leaf essential oil

Composition of Aloysia gratissima leaf essential oil

0031~!3422/%6 $3.00 + 0.00 Q 1986 Pergamon Press Ltd. Vol. 25, No. 6, pp. 1343-1345, 1986. Printed in Chat Britain. Phymhrmirrry. COMPOSITION OF AZ...

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0031~!3422/%6 $3.00 + 0.00 Q 1986 Pergamon Press Ltd.

Vol. 25, No. 6, pp. 1343-1345, 1986. Printed in Chat Britain.

Phymhrmirrry.

COMPOSITION OF AZDYSlA GRATISSIMA LEAF ESSENTIAL OIL* EDUMDO SQLeRtS, EDUARDODELLK.ASM~ and PATRICK MOYNA~$ t D&n Ltda, LasHem 17W,Montevideo, Uruguay; ~CXtatra de Fq

osia, Facultad de Quit&a, Avda Cknd

Ram

2 124,

Montevideo,Uruguay 27 Septtak

(Redsed reed Key Word ID&X--Abysb

gratiuimrr;

1985)

Verbenacea~ votetik leaf oil; sabinme; &inene; copaenol; cepaenone.

Abstract-Sabinene, &pinene, copaenol and copaenone have been isolated and identified in A. grad oil from plants growing in Uruguay.

INTRODIKtlON

and particularly genera tippia and Aloysia, and sub-tropical re8ions [I]. These genera are well known for their aromatic character [Z]. Their essential oils have been extensively studied in Brazil and Ar8entina Some species, like L cirric&ru HBK, are grown commercially for their use in perfumery [l J, while others are used in folk medicine [3--S]. One interesting aspect of their chemistry is the great diversity of compositions found. Such differences can exist in samples which are morphologically identical, and the existence of chemical races or the influence of climatic and gtogmphiCal conditions have been proposed as possible explanations [6,7]. These differences are usually limited to the substitution of a major component by another having an obvious chemical relationship 183, but in some cases there seem to be completely different compositions within the same morphologicat species [2,9]. Several species grow in Uruguay, five of which are woody. L. citricdora is cultivated as an ornamental plant. The other four, A. grutissima (Gill. et Hook.) Trot% A. sellowi Briq., A, c~~~~fol~ Chant. and A. virgata Ruix et Pav. [ 101 have not been previously analysed in spite of their interesting aromas. These species are native and usually gtow bordering rivers and streams. In this contribution we study the composition of the leaf essential oil from A. gratissima ( = A. lycioides = L. lycioides = A. ligustina = L. ligustrina [lo]) growing in Minas UrmPaY. Ve&naceae,

grow in tropical

RESULTS Taking into account the possibility of finding dramatic year to year variations due to climatic influences, samples from plants of the same population were colIected in two suocessive years at flowering time (October). Flowers were not included in the distillation. The essential oils were analysed by capihary GLC and the results are shown in Table 1. The identification of constituents was done by co-injection a+nst pure stan-

l

Complcral as partial requirement for the degree of'Doctor

en Qufmica’ of ES.

IeafessentiaI

dards, IR, NMR and GC/MS. As can be observed in Table 1, little chemical variation was observed in A. gra&sima leaf essential oils. More than 70% of the samples consisted of hydrocarbons (half of which were sesquiterpenes). The main constituent was sabinene (30x), with minor amounts of fl-pinene (8%). The oxygenated constituents were mainly sesquitetpenic alcohols and ketones. Oxygenated monoterpenes represented less than 6% of the total. Pinocamphone and isopinocamphone were identified, this being the first time that these compounds have been found in the group. Given the percentage of sabinene. it is interesting to note the very slight optical activity of the samples.

DISCUSSION

In Table 2 the average composition for A. grurissintu is compared with the published data for other species of these genera. We can observe that several groups can be established (for references, see notes in Table 2) (i) The most important, regarding the number of anaiysed species, is that of plants in which ketones are the main ~nstituents. Most of the species are from Argentina and none grows in Brazil. (ii) A second group is that of species where phenohcs are present+ all of them being found in Brazil. (iii) There is a third &roup formed by two species with high aldehyde contents, including L. citriodora (iv) The final group is that of species where hydrocarbons are important (in&ding mono- and sesquiterpenes) A. gratissima (h&as) f&s within this group, which includes all the other species described for BraxiL There is a clear relationship between A. grarisrimu (Minas) (30% sabinene) and L. aristata (21% sabinene, described for NE. Brazil). The composition found for A. gratis&ma growing in Minas is different from that of the species with the same morphological description growing in Argentina E191* EXPERIMENTAL

Generul.Fractional distillations were carried out in a SIRATA High Temperature Spinning Rand Cohnnn. Preparative GCs wm ccmpkted with a Rye UNICAM 1(# GC with progmmmed tempcratun Cspihsry CCs werecarried out in a Shim&u t3Cb 1343

E. SOLERet al.

1344

Tabk 1. Composition of A.grotfsrima leaf ecscntial oils

Compound 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 29 30 31 32 33 34 35 3p

a-Pincne j?-Pincnc Sabinenc o’TCZpinCiW2 LimO!lCllC 1,8-cincole p-Ciiene Terpinoknt a-Ekmene Pinocamphone C&b W’ W iso-Pin-phone

clcSabincne hyidrate a-Ccdrcnc Lw=Caryophyllene /I-Qryophyllcne Hydrocarbon Unknown unknown Unknown unknown &Cadincne @-Bisebolcnc Cd&. (M+ Cd&e (M+ unkIlown a-Chrmmm -t Cdb. fM+ frYw;~c

W 2041

204) cpo*

Copoenone Globulol or led01 ~~~~01 Copacnol Cls akohol

% (821’

% (83)

2.67 9.66 29.95 1.38 f.31 1.39 0.54 1.W 1.71 2.14 3.35 2.08 7.38 0.95 -

3.01 7.18 35.29 1.19 1.31 1.52 0.58 0.49 1.65 2.06 0.71 1.50 0.8 288 0.69 1.73 7.94 1.00 a36 Q36 0.77 1.08 2.08 1.23 O.% 0.37 1.81 1.22 1.34 0.89 1.54 4.14 3.08 0.81 428 1.54

2.0s

5.81 0.85 0.97 2.57 1.28 a50 0.50

1.93 3.59 3.48 1.10 4.29 3.87

Ment&kation t 1 1 1 1 1 1 1 4 4 2 4 2 4 2 4 1

2 2 2 4 4 4 4

3 3 3

3

4

3

4

3

4

Ref. 4 4 4

4

4 4 4 4, 4 4 4 4 2 4 4 2 4

3 3

4 4

Cl31 Cl41 Cl53

*Percentages arc w/w as detcrminatod by GC. t Identification key: 1, Rctcntion time on PEG 20 M anti OV 17; 2, *H NMR spsua; 3, IR; 4, GC!/MS.

AMPrF GC. Capillary columns were drawn with a Shim&u GDM-1 and co&cd with a Shimadxu MCI’-IA machine following ref. 1241.Rcfmctivc indexes wcrc dctcrmincd with an ATAGG M Rcfractometa. Gptical rotations were mcasurcd u~b1f3 50 mm aUs a2tdan ATAGG poku pofarimctn. IR spcetra wererun neat on NaCl dima, on a P&in-Rlmer 177.NMRs on a Varian T-60 using CCL as solvent. GC/MS wcrc measud on a Hitachi M-80 GC/MS with an ionization potential of 20 eV. All solvents were distilled in @as5 prior to their use. AU other ~~~~Of~~~~ P&m material. Young twigs of A. $pXlt~ wem collestcd from wild plants growing 2Okm SW of Minas, Uruguay. Ck&ctions were carried out during the flowering pcriads On 11/10/82and13/10/83.Tbekavcswerepickedbyhandaftcr3 day6 at room temp.

D~tf~~. The dry lcaWs wcrc stcamdistiRcd. The condcnacd HxO was separated from the supcrnatant oil and cxtractcd with RtzO, The ethereal extract was W to the oily laycr,dried (NarSG,) and evaporated to yield a greenish oil. For

1982 the yiekl was 1.6% (v/w; 10.5ml from 65Og leaves; d, = 0.9002; [a]r = 0”. RI = 1.4g76), and for 1983, 1.9% (v/w; 14.1ml from 750 leaves;d, = 0.8997; !zg = - 1”;RI = 1.4874). Fractionaf ~~i~~t~ The essenti oil (35 ml) was distilled under vacullm. The system was l&St r&lxcd closed for 30 min. The r&x ratio was then set at 40, with a distillation-rate of 5 ml/br and a band-spaed of 2000 rpm. Four fractions were distill& at 8 mm Hg within a range of 40-S0”;threeatSmanHgaMlarangeof45Sa;~atLSmmHg and a range of 60%0”. All fractions were then adysed by

capillary GC and cxamincd against the original oil to detect the presuW of artifacts. c01amvJ c~~~ru~y. Column chromatography was car&d out with silica gel (Merck lOlSl), using a SO/l ratio of silica to sample. Hydrocarbons wcm elutd with petrol (bp 60-70*), and the oxygcnatcd fractions elutcd with increasing pcnrntagcs of Me&G. Arggntntfon c&nn clergy. Hydrocarbon fractions were resolved on silica gc1 with 10% AgNOl added.

1345 Lippia and A&ysia ascntial oils by groups of components

OiO compounds 01 Ket

Species

H

L.. alba B.

5.3

L.. L. cittiora grata

A. pdystochia

48.5 1.4 44.4 3.8 36.3 220 26.0 30.0

11.6 0.6 1.6 1.8 7.2 -

L.. L. &ensis grisrbcrquw

15.0 16.5

L. afl aristata L.-is L. aristata A. gratissima

24.8 9.5 423 47.0

L. sidoides

L.ahifblia L jbicalis

LalbaA.

A.lycioi&s

0, s compounds Gx Phm

Ref.

Al

H

22.5

33.3

-

0.6 60.4 61.0 52.0 70.0

59.4 -

-3.5 9.7 41.0 1.8 6.2 -

-

47.0 4.1

69.5 22.0

-0.3

-5.3

-

-

i::;

0.8 35.1 1.2 -

36.5 4.0

-

-4.5 15.8

t

:;I 121

-

-

65.8 7.3 46.1 14.7

43.1 48.6 34.8 -

PI

::

PI

121

[173

11’31 1191t 1203

*Key: H, hydrocarbow 01. akohols; Ket, ketones; Aid, aldehydts; Ox, oxygenated compounds; Phen, phenols. t Sa comment.9 in Discussion.

Gas chromatography.Analytiad GLC was carried out with WCGTs: (a) stainless steel, FFAP, i.d. 0.25 mm, 45 m; (b) glass, PEG 2OM, i.d. 0.3mn1, 30m; (c) OV-17, id. 0.5mm, 60m. Injection and detector temps were 250”.column oven temp. from 60 to [email protected]’at 6”/min; carricr: Ns at 30 ml/min; splitter ratio 32 Preparative GLC was carried out t&l8 8lass Cohmms (GV-101 5 % on Diatomite CAW DMCS 80-90 me&), of 4.6 m length, i.d. 8 mm; carrier: NI at 100 ml/min, using a 1/lOO splitting ratio, with CC&/Me&O cold-traps. Acknowkdgenrents-The authors wish to thank IFS (Stockholm) for 8rants No. F434 and No. F741 whkh made their work possible. We also acknowledge the collaboration of Prof. B. ArriUa8a de Ma&i (Botany Lab. Facultad de Quimka, Montevideo) for the identifkation of the plant samplta; of Prof. 0. Clark (IGCD-Univ. Missouri, U.SA.), Mr. T. Iwai (Talrasrgo PC, Tokyo, Japan), and Dr. A. F. Thomas (Firmenkh R&D, Geneva, Switxerland), for samples and GC/MS data, togaher with very useful and valuable comments and sugscstions; of the Japanese Embassy at Montevideo. for an important equipment grrrnt to the Facultad de Quimica; of the Centro Coopcrativista dcl Uruguay, for their support during the initial StagtJ of the projact. REFERENCES

1. Bezrra, P, Fernandes, A. G, Cravciro, A. & Andradc, C. H. S., Mates, F. J. A, Alencar. J. W, Me&do. M. I. L. Vii G. S. B., Mates, F. F. and Rouquayrol, M. 2 (1980) Cmnposicao Q&mica e A~iuidade Biologica de Oleos Essex&is de Plankas do Nordesu-gemro Lippia Vlth Simp6do de Plantas Medkinais do Bra&l, Fort&m. 2 Craveiro, A. A.. Akncar. J. W., Mates, F. J. A., And&c, C. H. Sand Ma&do. M. I. L. (1981) 1. Not. Prod. 44,598. 3. Viana,G.SB,Matos,F.J.A.andCraveiro,A.A.(198O)C&n. Cult. (supl.) 32, 752.

4. Pellccuer, J, Jacob, M, Sin de Bouchber& M, Dusart, G.. Attiso. M.. Bartha. M, Gour8as, L., Pascal, B. and Tomei, R. (1980) Plant. Med. Phytotha. 14.83. 5. Viana, G. S. B.. Mates, F. F.. Araujo. W. L., Mates, F. J. A. and Craveiro. A. A (1981) Q. J. Crude Drug. Rex. 19. 1. 6. Dell& A. A. and Retamar, 1. A. (1974) Essenze De&. Agruwmri 44.23. 7. Rio&di, A. I. A. (1976) Bol. SAIPA 22,3. 8. Huer8o. H. H. and Rctamar, J. A. (1973) Arch. E&l. Quim Farm UNT 18,15. 9. Catalan, C. A. N., Merep, D. 1. and Retamar, J. A. (1977) Riv. Ir. EPPOS S9, 513. 10. Lombardo, A. (1964) Flora Arborea y Arbmescente del Uruguay. IMM, Montevideo. 11. Forscn,K.andSchan~M.V.(1971)Arch.Phmm30J.944. 12. Na& P. and Kaiser, R. (1972) Tetrahedron Letters 2013. 13. Nishimura, H. and Calvin. M. (1979) Agric. Food. Chem 27, 432 14. Mod, 0, Rep&, M. and !IaImcra, P. (1977) Arch. Phmm 310.75. 15. Taskinen, 1. (1975) Acta Ghan SC&. B 29,999. 16. Brasil e Silva, A., de Assis, G, Baua, L, Saravia de Siqueira, N. C., Morcira, C T. and Santana B&is, M. S. (1979) Trib. FUIWL(Curitiba) 47.96. 17. Retamar. J. A., Taknti, B. C. J. and Deffini, A. A. (1975) Essenze Derb. Agrum 631. 18. Catalan,A.N,Mercp,D.I.andRetamar,J.A.(1977)Riu.It. EPPOS 59,513. 19. Riscala, E. C, Talenti, E. C. I. and Retamar, J. A. (1973) Esseme Deriu. AgMn 43.291. 20. Rctamar. J. A. (1981) Esseme Derio. Agrum 51, 109. 21. Rovesti, P. (1972) Rb. It EPPOS 54,254. 22 Rctamar, J. A. (1981) Easerue Deriu. AgNm 51.91. 23. Cho8o. J. and Crank, G. (1982) 1. Nat. Prod. 45,186. 24. Grab, K. and Grob, G. (1976) 1. Chromatogr. 12S, 471.