The Volatile Oil of Ziziphora: Hispanica

FLAVOUR AND FRAGRANCE JOURNAL, VOL.
1, 111-113 (1986)
The Volatile Oil of Ziziphora hispanica L.

A. Velasco Negueruela
Departamento de Boihica y Fisiologfa Vegetal, Facultad de Biolog(a, Universidad Complutense, Madrid, 28040, Spain
M. Mata Rico
Departamento de Farmacognosia y Farmacodinamia, Facultad de Farmacia, Universidad Complutense, Madrid, 28040, Spain
Analysis of the steam-volatile leaf and flower oil of Ziziphora hispanica L. by gas-chromatography (GC)
confirmed that pulegone and piperitenone are the main monoterpenes. Lesser amounts of limonene, 1,%cineole,
isopulegol, trans-isopiperitenol and thymol are present. 8-Cadinene is the main sesquiterpene together with
caryophyllene oxide and cis-nerolidol. The pulegone content of the oil tended to increase before flowering and
decrease once flowering had commenced.
KEY WORDS Essential oil Ziziphora hispunicu L. Lamiaceae Pulegone Piperitenone
INTRODUCTION in the author's laboratory.293We have also used

infra red spectroscopy (IR) and l3C-nuclear
Previous chemical investigations of the con- magnetic resonance (I3C-NMR) analysis for
stituents of the foliage and flowers of Ziziphora further identification.
hispanica L., an endemic of the central region of Pulegone, piperitenone and cis-piperitone
Spain, indicated the presence of pulegone and oxide were also identified by ultraviolet spectro-
piperitenone.' It was decided to reinvestigate the scopy (UV) and by analytical thin-layer
steam volatile oil using GC to identify the further chromatography (TLC).
components present in the oil. Component concentrations were calculated
from GC peak areas without using a correction
factor.
EXPERIMENTAL
Three samples of Ziziphora hispanica were har- TL C

vested, one prior to flowering (ZHNF) and the
other two during flowering (ZHF1 and ZHF2) This was performed on pre-coated silica gel
near Arganda, Madrid, in the central part of plates4 using MeC6HS:EtOAc (93:7) as solvent.
Spain. Dry leaves, stems and flowers were Detection with vanillin-sulphuric acid gave the
hydro-distilled in a Clevenger apparatus. The following results: piperitenone (R, 0.26),
mean yield of the oil was 1.38% based on dry piperitone (R, 0.31), isomenthone (R, 0.65),
weight of sample. pulegone (R, 0.50) and menthofuran (R, 0.95).
Voucher specimens were deposited in the Her-
barium of the Facultad de Biologia, Universidad
Complutense de Madrid (M.A.C.). Preparative Thin-layer Chromatography
This was performed on silica gel 60 PFz54(E.
Merck no. 7747), layer thickness 2mm, using
Identification of Components 1 ml of sample. After detection by UV
Most of the individual components were tenta- (254-360 nm), pulegone, piperitenone,
tively identified by comparing their retention piperitone and cis-piperitone oxide were isolated
times (R,) with those of pure standards available using chloroform.
0882-5734/86/030111-03SO5.00 Received 29 April 1986
0 1986 by John Wiley & Sons, Ltd. Accepted 19 August 1986
I12 A. VELASCO NEGUERUELA AND M. MATA RICO
GC IR
Analytical G C was carried out on a Perkin-Elmer Spectra were performed on a Pye-Unicam SP 200
3920 gas chromatograph fitted with either ( 1 ) and were run as liquid films, NaCl cell
stainless steel column 2 m x 3.18 mm, packed (0.025 mm). For further identification the 1R
with UCON LB 550 X or (2) stainless steel spectra were performed directly on the essential
column 2 m x 3.18 mm, packed with APIEZON oil sample as in reference 11.
L Detector used dual FID, carrier gas He, flow
rate 30 ml/min, temperature programmed
95"C-180°C/min, injector temperature 200°C, W-N M R
detector temperature 2S0°C, injection volume for Analysis was performed directly on the essential
all samples 0.04 pl. The quantitative composition oil sample as in reference 12, on a Varian XL 300
(relative percentages) was obtained in a comput- spectrophotometer, solvent used ChDhr fre-
ing integrator Varian SP 4270. quency 300 MHz, internal standard TMS. The
values for the individual components of the oil
were consistent with those reported."
uv
The spectra were performed on a Perkin-Elmer RESULTS AND DISCUSSION
Hitachi 200 spectrophotometer, recorded in
E,OH. A,, found were consistent with those in the The percentage composition of the oil and the
identification methods are given in Table 1, Com-
Table 1. Volatile components of Ziziphora hispanica L.
Percentage composition
Component ZHFl ZHF2 ZHNF Identification method
a-Pinene 0.30 0.30 0.35 "C-NMR. RT

Camphene 0.01 RT
P-Pinene 0.32 0.31 0.45 RT
Myrcene 0.1 1 RT
6-Car-3-ene 0.02 0.02 RT
Limonene + 1 ,8-Cineole 1.90 2.55 3.58 "C-NMR. RT
pCymene 0.80 0.04 I3C-NMR, RT
y-Terpinene 0.68 0.01 I3C-NMR, RT
Terpinolene 0.33 0.02 "C-NMR, RT
Octan-3-01 0.34 0.01 0.01 13C-NMR, RT
Oct- 1-en-3-01 0.44 0.18 0.13 I3C-NMR, RT
cis-allo-Ocimene 0.94 0.04 0.03 RT
a-Thujone 0.57 0.06 13C-NMR, RT
rrans-Thujan-4-01 0.10 0.08 0.01 RT
Menthofuran 0.66 0.39 0.28 "C-NMR,RT, TLC
Isopulegol 1.33 0.74 0.98 "C-NMR, RT
!runs-Dihydrocarvone 0.15 0.04 RT
Menthol 0.42 0.28 0.12 "C-NMR, RT
Pulegone 64.57 62.69 76.66 1R. UV, I3C-NMR, RT, TLC
Piperitone 0.10 0.04 0.01 IR, UV, "C-NMR, RT, TLC
cis-Piperitone oxide 1.02 0.60 0.25 IR, UV, RT
Nerol 0.27 0.44 0.20 I3C-NMR, RT
rrans-Isopiperitenol 2.71 1.47 0.42 RT
Piperitenone 15.64 16.67 11.65 IR, UV, RT, TLC
Thymol 0.97 0.97 0.31 I3C-NMR, RT
cis-Nerolidol 1.31 0.22 RT
Caryophyllene oxide 1.46 0.50 RT
Humulene oxide 1.13 0.52 RT
6-Cadinene 2.03 1.79 0.25 I3C-NMR, RT
VOLATILE OIL OF ZIZIPHORA HlSPANlCA L. 113
ponents were arranged in order of GC elution 2. A. Velasco Negueruela and M. J. Perez Alonso. Anales
(UCON). Jard. Bot. Madrid, 40(1), 107 (1983).
3. A. Velsaco Negueruela, M.J. PCrez Alonso and M. Mata
From these results we may note that Rico, Anal. Bromatol., 34(2), 231 (1983).
piperitenone, the biogenetic precursor of 4. H . Wagner, S. Bladt and E. M. Zgainski, Plant Drug
p ~ l e g o n e , ' ~increases during flowering. This Analysis. Springer Verlag, Berlin (1984).
might well mean that the stereospecific reduction 5. J. Wiemann and Y. Dubois, Bull. SOC. Chim. France, 5,
1813 (1962).
of piperitenone to pulegone is blocked during 6. R. H. Reitsema and V. J. Varnis, J . A m . Chem. SOC., 78,
flowering (substrate inhibition of the enzyme?) 3792 (1955).
This oil is of interest for the high content of 7. I . A. de Iglesias and J. A. Retamar, Riu. Italiana
pulegone. Our results are in good agreement E. P. P. 0. S., 60(10), 548 (1978).
with that p r o p o ~ a lthat' ~ piperitenone is the bio- 8. Y.-R. Naves, Riu. Italiana E. P. P. 0.S . , 58, 136 (1976).
9. R. H. Reitserna, J . A m . Chem. SOC., 78, 5022 (1956).
genetic precursor of pulegone. 10. K. L. Handa, D. M. Smith, I. C. Nigam and L. Levi, J .
Pharm. Sci., 53(11). 1407 (1964).
Acknowledgement-We wish to express our very grateful 11. J. Bellanato and A. Hidalgo, Infrared Analysis of Essen-
appreciation to Dr M. P. Pardo and Dr M. T. Ortega for tial Oils, Heyden, London (1971).
collecting and providing sample ZHl and for valuable per- 12. V. Formitek and K.-H. Kubeczka, Essential Oil Analysis
sonal communications. by Capillary Gas Chromatography and Carbon-I3 NMR
Spectroscopy, John Wiley, New York ( 1 982).
13. 9 . M. Lawrence, A study of the monoterpene interrela-
tionships in the genus Mentha with special reference to
REFERENCES the origin of the pulegone and menthofuran, doctoral
thesis, Rijksuniversiteit te Groningen, The Netherlands
1. M. P. Pardo and M. T. Ortega, X V Congreso Interna- (1978).
cional de la SOC. Farm. del Mediterrlineo Latino, Palermo
(1 982).

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FLAVOUR AND FRAGRANCE JOURNAL, VOL.

The Volatile Oil of Ziziphora hispanica L.

KEY WORDS Essential oil Ziziphora hispunicu L. Lamiaceae Pulegone Piperitenone

INTRODUCTION in the author's laboratory.293We have also used

Three samples of Ziziphora hispanica were har- TL C

Table 1. Volatile components of Ziziphora hispanica L.

Component ZHFl ZHF2 ZHNF Identification method

a-Pinene 0.30 0.30 0.35 "C-NMR. RT

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