J. Agric. Food Chem.

1996, 44, 217−222 217

Sesquiterpenic Epoxides and Alcohols Derived from Hydrocarbons

of Vetiver Essential Oil
Isabelle Bombarda,† Emile M. Gaydou,*,† Jacqueline Smadja,‡ and Robert Faure|
Laboratoire de Phytochimie de Marseille, Faculté des Sciences et Techniques de Saint Jérôme,
Avenue Escadrille Normandie Niémen, 13397 Marseille Cedex 20, France, and Laboratoire de Chimie
Organique, Université de La Réunion, Avenue René Cassin, 97490 Saint-Denis Cedex, France

Increasing the value of the hydrocarbon fraction of Bourbon vetiver essential oil (BVEO) was
attempted by oxidation and reduction reactions to obtain odorous sesquiterpenic alcohols. Oxidation
of this sesquiterpenic fraction of BVEO with m-chloroperbenzoic acid afforded three new oxidized
products, including a zizaene monoepoxide and two diepoxides derived from zizanene and valencene.
Reduction reaction of sesquiterpenic epoxides of BVEO led to three sesquiterpenols, including two
zizanol epimers and an epoxialcohol derived from valencene, which have been synthesized in high
yields (85-100%). Structural determination of these derivatives followed from one- and two-
dimensional NMR spectroscopy and gas chromatography-mass spectrometry techniques.

Keywords: Essential oil; vetiver; sesquiterpene; epoxide; sesquiterpenol; oxidation; reduction; 2D-
NMR; MS

INTRODUCTION cumene, germacrene D, and R-humulene (Weyerstahl

et al., 1986; Maurer and Hauser, 1982; Iwamuro et al.,
Some oils have a high content of terpenes and are 1981). Furthermore, good stereoselectivity was ob-
proposed as “monoterpeneless oil” for perfumery and tained in the case of prezizaenes, β-selinene, and R-gur-
aromatic industries because these components change junene (Nagashima and Yoshida, 1981; Richardson et
oil quality. The oxygenated fraction of these oils al., 1991; Palmade et al., 1963).
exhibits interesting odors for perfumery purposes, Bourbon vetiver essential oil (BVEO), considered as
whereas the hydrocarbon fraction is of lower commercial the best vetiver essential oil in the world for its
value. Ylang extra or first, which contains 70% oxygen- exceptional olfactory qualities, is used in many perfumes
ated compounds, is used in many perfumery formula- known as “top quality goods” (Ganguly et al., 1978;
tions and ylang third, which contains 70% sesquiter- Garnero, 1971). From a chemical point of view, this oil
penic hydrocarbons (Gaydou et al., 1986, 1988), is is extremely complex and particularly rich in sesqui-
generally used in toiletry products. To minimize dete- terpenes. More than 150 compounds, with 11 different
rioration of oil quality and increase oil stability, several sesquiterpene skeletons, have been characterized (Nguy-
methods have been developed, in particular for Citrus en and Fetizon, 1963; Sabetay and Trabaud, 1939, 1942;
essential oils that are rich in limonene (Ferrer and Smadja, 1991). In this work, we describe an oxidation
Matthews, 1987; Moyler and Stephens, 1992; Tzamtzis of the resulting hydrocarbon fraction of vetiver oil.
et al., 1990). In our case, we took an interest in the
terpenic hydrocarbon fraction that is a by-product of
MATERIALS AND METHODS
aromatic industries. With this aim in view, we first
performed an oxidation reaction and then a reduction Sampling and Origin of BVEO. All BVEO samples were
reaction of this hydrocarbon fraction to obtain sesqui- obtained from a local distillery near Manapany-les-Hauts
terpenols, which should have potentially interesting (south of Reunion Island, France).
fragrances for perfumery. Fractionation of BVEO. The hydrocarbon fraction was
obtained by column chromatography (CC) of BVEO. The
Several reagents have been used to oxidize sesqui- BVEO (5-10 g) was submitted to CC over silica gel 60 (215 g,
terpenic compounds into sesquiterpenols, particularly 230-400 mesh, E. Merck) using an 80-cm column (30 mm i.d.).
molecular oxygen (Shieh and Matsubara, 1981; Ter Elution of the hydrocarbon fraction containing compounds 1-3
Heide et al., 1988; Kazuo and Masaaki, 1979) or metal was carried out with 450 mL of pentane (yield 30%). The
acetate (Haruo et al., 1978; Iwamuro et al., 1981; oxygenated fraction was eluted with 600 mL of diethyl ether.
Tkachev et al., 1983). But these methods lead to many Oxidation of the Hydrocarbon Fraction. m-Chloro-
by-products, and yields are generally low. Sesquiter- perbenzoic acid (MCPBA; Fluka Chemicals, Switzerland) was
pene oxidations are also done with carboxylic peracids, used as the oxidant. In the different experiments, a solution
in particular with m-chloroperbenzoic acid. This method of BVEO sesquiterpenic fraction (100 mg-1 g) in methylene
chloride (2-20 mL) was stirred at 0 °C during the addition of
offers many advantages because epoxides were obtained small aliquots of MCPBA (1 equiv) in methylene chloride. The
in high yields (Tressl et al., 1983; Bombarda et al., 1994). reaction mixture was allowed to stand for 20 min to 1 h.
Good regioselectivity was obtained in the case of β-cur- Unreacted MCPBA and byproduct m-chlorobenzoic acid were
removed by addition first of an aqueous solution containing
10% sodium sulfite and then 10% sodium bicarbonate. The
* Author to whom correspondence should be ad-
organic layer was then concentrated under reduced pressure
dressed [telephone and fax: (33) 91 28 86 47]. on a rotavapor. The crude products contained epoxides 4
† Laboratoire de Phytochimie de Marseille.
[(1S,2S,5S,8R)-6R,13-epoxy-2,7,7-trimethyltricyclo[6.2.1.01,7]-
‡ Laboratoire de Chimie Organique.
undecane; 7-9%] and 5 [(1S,2S,5S,8R)-6β,12-epoxy-2,7,7-
| Present address: U. R. A. 1411, Faculté des Sciences
trimethyltricyclo[6.2.1.01,7]undecane; 6.5-13%] and diepoxides
et Techniques de Saint-Jérôme, Marseille, France. 6 [(1R,6R,10S)-(2R,3R),(7β,8β)-diepoxy-3,7-dimethyl-10-isopro-

0021-8561/96/1444-0217$12.00/0 © 1996 American Chemical Society

218 J. Agric. Food Chem., Vol. 44, No. 1, 1996 Bombarda et al.

pylbicyclo[4.4.0]decane; 7-9%] and 7 [(5S,6R)-5,6-dimethyl-

1R,2R-epoxy-8(13,13-dimethyl-8R,13R-epoxy) isopropylbicyclo-
[4.4.0]decane; 5-7%]. [Relative percentages were obtained by
gas chromatography (GC), vide infra.] After purification, the
products were submitted to NMR spectroscopy and GC-MS.
Purification of Epoxide 5. The crude epoxide mixture
(643 mg) was submitted to CC over silica gel 60 (50 g, 230-
400 mesh, E. Merck) using a 30-cm column (25 mm i.d.).
Elution was carried out with 90:10 (v/v) pentane:diethyl ether
(500 mL) and collected in 50 tubes. Tubes 23-25 (tube
volume, 10 mL) contained 17 mg of epoxide 5 (72% purity by
GC; Rf, 0.68).
Purification of Diepoxide 6. A solution of BVEO ses-
quiterpenic fraction (150 mg, 0.74 mmol) was reacted with
MCPBA (257 mg, 1 equiv) at 0 °C for 20 min. The reaction
mixture (120 mg) containing 7% of 4, 6.5% of 5, 9% of diepoxide
6, and 6% of 7 was fractionated by CC with 70:30 (v/v) pentane:
diethyl ether (500 mL) and collected in 50 tubes. Tubes 20-
21 (tube volume, 10 mL) contained 9 mg of diepoxide 6 (80%
purity by GC; Rf, 0.65).
Purification of Diepoxide 7. A solution of BVEO ses-
quiterpenic fraction (650 mg, 2.92 mmol) was reacted with
MCPBA (786 mg, 1 equiv at -30 °C for 30 min. The crude
product containing 11.2% of 4, 28.5% of 5, 11.6% of 6, and
10.5% of 7, was submitted to CC. Elution of the monoepoxide
fraction containing 4 and 5 was carried out with 300 mL of
pentane:diethyl ether (90:10, v/v). The diepoxide fraction was
eluted with 100% diethyl ether (400 mL). This second fraction
(181 mg), containing 9% of 6 and 23% of diepoxide 7, was
submitted to CC. Elution was carried out with 60:40 (v/v)
pentane:diethyl ether (500 mL) and collected in 50 tubes (tube
volume, 10 mL). Tubes 37-41 (42 mg) contained 20% of
diepoxide 6 and 63% of diepoxide 7. This mixture was
submitted to a new purification by CC with 50:50 (v/v) pentane:
diethyl ether (150 mL) as eluant. Tubes 16-17 (10 mg)
contained diepoxide 7 (75% purity by GC; Rf, 0.55).
Reduction Procedures. The sesquiterpene epoxides or
oxidized hydrocarbon fraction (220 mg; 1 mmol) were reduced
with lithium aluminium hydride (LiAlH4; Fluka Chemicals,
Switzerland; 152 mg, 4 equiv) in refluxing tetrahydrofuran
(THF; 10 mL) for 12 to 36 h. The complex LiAl-alcoholate
was hydrolyzed with 10% sulfuric acid, and reduction products
were obtained by extraction of the solution with diethyl ether.
The reduction reaction with lithium triethyl borohydride
(LiEt3BH, Aldrich Chemical Company Inc.) was achieved by
the method of Brown et al. (1980) under helium atmosphere.
Sesquiterpene epoxides (220 mg, 1 mmol) in 3 mL of THF were
added with a syringe to a solution containing 2 mL (2 mmol,
2 equiv) of a 1 mol L-1 solution of LiEt3BH in 1 mL of THF.
The mixture was vigorously stirred at room temperature. Figure 1. Gas chromatogram of (a) BVEO, (b) hydrocarbon
After 12 h, the reaction mixture was hydrolyzed with 1 mL of fraction of BVEO, and (c) oxygenated hydrocarbon fraction of
BVEO, obtained by GC on Carbowax 20 M column.
water. The triethylborane formed was oxidized with 1 mL of
30% hydrogen peroxide. The aqueous phase was extracted
cation was by CC with 40:60 (v/v) pentane:diethyl ether (100
with 2 × 5 mL of diethyl ether. After volatile material
mL collected in 20 tubes) as the eluent. Tubes 12-13
evaporation under reduced pressure, the crude material was
contained 14 mg of epoxialcohol 10 (95% purity by GC; Rf,
analyzed by GC and then by NMR and GC-MS. 0.50).
Reduction Reaction of Epoxides 4 and 5. A mixture of GC and GC-MS. A Delsi 300 gas chromatograph equipped
epoxides containing 25% of 4 and 55% of 5 was reduced with with a flame ionization detector (FID) was used for compound
LiAlH4 (4 equiv) in refluxing THF for 24 h or with LiEt3BH (2 separations with a fused silica capillary column (0.32 mm i.d.)
equiv, ambient temperature, 12 h). Alcohols 8 [(1S,2S,5S,8R)- coated with Carbowax 20 M (25 m; phase thickness, 0.20 µm;
2,7,7-trimethyltricyclo[6.2.1.01,7]undecan-6R-ol)] and 9 [(1S, column temperature, 170 °C or 60 to 220 °C, 4 °C‚min-1).
2S,5S,8R)-2,7,7-trimethyltricyclo[6.2.1.01,7]undecan-6β-ol] were Detector and inlet temperatures were 250 °C. Helium was
obtained (25% and 46% yields, respectively). This mixture was used as carrier gas at an inner pressure of 0.4 bar. The
fractionated by CC with 40:60 (v/v) pentane:diethyl ether (250 injections averaged 1 µL of a 2% solution of crude mixtures in
mL, collected in 30 tubes). Tubes 15-16 contained 6 mg of pentane. Combined GC-MS was recorded on a Delsi gas
alcohol 8 (91% purity GC; Rf, 0.78) and tubes 18-19 contained chromatograph linked to a Ribermag R-10-10C mass spec-
21 mg of alcohol 9 (94% purity by GC, Rf, 0.75). trometer equipped with a quadrupole mass analyzer (15.6 mm
Pure epoxide 5 (31 mg, 0.14 mmol) was reduced with LiAlH4 i.d. × 350 mm, 10-6 mmHg) and coupled to a Sidar data
(22 mg, 4 equiv) in refluxing THF for 24 h. Alcohol 9 was computer. The GC column was a 0.32 mm (i.d.) × 25 m fused
obtained with 85% purity by GC. capillary column coated with Wax 51 (0.20 µm phase thick-
Reduction Reaction of Diepoxide 7. Diepoxide 7 (20 mg, ness). The column temperature was changed from 150 to 220
0.08 mmol) was reduced with LiEt3BH (2 equiv, ambient °C, at a rate of 3 °C min-1, the carrier gas was helium, the ion
temperature, 12 h). Epoxialcohol 10 [17 mg, 5,6-dimethyl-8- source was 220 °C, and the ionizing voltage was 70 eV.
(13,13-dimethyl-8R,13R-epoxy)isopropylbicyclo[4.4.0]decan-1R- Thin-Layer Chromatography (TLC). Analytical TLC
ol] was obtained with 91% purity by GC (89% yield). Purifi- was performed on precoated plates (5 × 10 cm, silica gel 60
Sesquiterpenic Epoxides and Alcohols from Vetiver Oil J. Agric. Food Chem., Vol. 44, No. 1, 1996 219

Figure 2. Structures and carbon numbering for NMR analysis of sesquiterpenes 1-3, epoxides 4-7, and corresponding reduction
compounds 8-10.

F254, 0.25 mm, Merck). Spots were visualized by examination ally associated with prezizaene, a precursor of zizaene
under UV light and/or sulfuric acid spray reagent (5% solution (Andersen and Falcone, 1970). Valencene is a common
of sulfuric acid in diethyl ether) followed by brief heating. sesquiterpene of various essential oil (Masada, 1976),
NMR Spectroscopy. All NMR spectra were recorded on but zizanene is a typical sesquiterpene of vetiver (Gar-
a Bruker AMX-400 spectrometer. The 13C and 1NMR spectra
nero, 1971).
were measured as solutions in chloroform-d in 5-mm o.d. tubes.
Tetramethylsilane was used as internal standard in both In the presence of MCPBA, zizaene (1) led to the two
measurements. Proton-proton coupling constants were ex- corresponding zizaene epoxide epimers 4 and 5 (Figure
tracted from high-field resolution-enhanced 1H NMR spectra 2) in a ratio 0.9:1.1, as observed by GC analyses (Figure
by the Gaussian multiplication technique (Ferridge and Lin- 1c). Among the four stereoisomer epoxides of zizanene
don, 1978). Resonance multiplicities for carbon-13 were (2) expected, the (2,3)R-(7,8)β-diepoxide 6 (Figure 2) was
established via the acquisition of DEPT spectra (Doddrell et the main product, as confirmed by spectroscopic struc-
al., 1982) obtained for proton pulses, P ) 90° (CH only) and P ture determinations (Figure 2). This compound cor-
) 135° (CH and CH3 differentiated from CH2). Standard responded to R and β attacks on 2,3 and 7,8 double
Bruker pulse sequence were used for homonuclear and het- bonds, respectively, by the oxidant reagent. The main
eronuclear correlation experiments. For other experimental
details, see Faure et al. (1991).
attack site by MCPBA during epoxidation of valencene
(3) is on the R face of two double bonds to yield the
valencene diepoxide 7 (Figure 2). In fact, the β face is
RESULTS AND DISCUSSION
hindered by the CH3-11 and CH3-12 groups.
Hydrocarbon Fraction Oxidation of BVEO. A The retention time and mass spectral data of 5, 6,
hydrocarbon fraction representing 30% of BVEO was and 7 are given in Table 1. The 1H and 13C chemical
obtained by fractionation of the oil by CC. The gas shifts are given in Table 2 for 5, Table 3 for 6, and Table
chromatograms of BVEO and hydrocarbon fraction are 4 for 7, and the 1H-1H coupling constants are given in
given in Figures 1a and 1b, respectively. The oxidation Table 5.
reaction of BVEO hydrocarbons was achieved with Reduction of Epoxides 4-7. Reduction of the
m-chloroperbenzoic acid (MCPBA) at various hydrocar- oxidized hydrocarbon portion with lithium aluminum
bon:MCPBA ratios (1:1 to 1:3) because some of the hydride (LiAlH4) or lithium triethylborohydride (Et3-
hydrocarbons have more than one double bond. The gas BHLi) led to three major alcohols, 8, 9, and 10, repre-
chromatogram of the oxidized products were, similar for senting 25% of the mixture (Figure 1). Structures of
each experiment (Figure 1c). Among the reaction these sesquiterpenols are given in Figure 2. Zizanene
mixture, four oxidized compounds (4-7) were obtained diepoxide 6 was not reduced by LiAlH4 or Et3BHLi, and
in high yields. These oxidized compounds were isolated only the 1,2-epoxide of valencene diepoxide was reduced
and their structures determined by NMR spectroscopy. in the corresponding R-ol 10. Alcohols 9 and 10 had
The structures of the compounds isolated suggested that been isolated when a reduction reaction was achieved
the more reactive sesquiterpenes contained in the with pure 5 and 7. Alcohol 8 was isolated from the
hydrocarbon fraction were zizaene (1), zizanene (2), and reduction reaction of a mixture of 4 and 5. The
valencene (3; Figure 2). These compounds represent the structure of 4, which is zizaene epoxide (an epimer of
major sesquiterpenes as given by Garnero (1971). Ziza- 5), has been specified on the basis of the structure
ene is a sesquiterpene commonly found in vetiver determination of the sesquiterpenol 8. This reaction
essential oil (Nguyen and Fetizon, 1963), and is gener- was regioselective, with hydride attack on the less
220 J. Agric. Food Chem., Vol. 44, No. 1, 1996 Bombarda et al.

Table 1. Retention Times and Mass Spectra of Oxidation-Reduction Products of BVEO

compda IRb mass spectral datac
5 1810 M+ 220, 41(100), 105(50.3), 91(47.4), 55(43.6), 205(42.6), 43(34.6), 177(34.6), 133(32.7), 124(31.9), 93(30.4), 79(30.0),
29(29.2), 39(26.9), 119(24.8), 67(24.3), 109(24.2), 95(23.5), 175(23.2), 107(23.1), 77(21.4), 220(20.1), 53(20.0)
6 2000 M+ 236, 43(100), 41(41.7), 55(23.9), 95(22.8), 193(22.3), 109(21.4), 105(20.8), 107(18.9), 93(15.5), 39(13.8), 53(12.0),
91(11.8), 81(11.7), 79(11.6), 29(11.3), 67(10.3)
7 2135 M+ 236, 41(100), 43(90.0), 221(64.5), 55(57.6), 93(51.1), 179(36.6), 81(32.6), 109(31.1), 53(30.7), 105(29.3), 79(25.9),
95(25.1), 119(25.0), 107(22.8), 67(22.3), 39(21.9), 29(20.6), 161(20.6)
8 1893 M+ 222, 43(100), 41(51.0), 71(50.8), 109(36.8), 95(30.6), 179(29.9), 82(28.4), 67(21.9), 55(21.5), 189(18.2), 69(17.4),
93(15.9), 107(15.6), 137(15.5), 81(14.3), 91(13.0), 79(12.1), 29(11.5), 135(11.3), 161(11.0)
9 1818 M+ 222, 43(100), 41(89.0), 109(55.6), 84(45.8), 69(45.4), 95(44.7), 179(41.5), 71(39.2), 55(30.3), 67(27.8), 93(27.8),
161(27.8), 207(27.2), 81(23.3), 91(22.0), 79(21.2), 107(20.8), 29(19.5), 105(17.6)
10 2309 M+ 238, 43(100), 41(91.4), 122(83.7), 55(61.9), 107(60.6), 109(50.2), 111(38.6), 81(36.5), 95(36.3), 105(28.4), 123(28.4),
93(27.0), 205(26.6), 91(26.0), 223(25.4), 29(24.6), 121(24.3), 147(24.1), 59(23.9), 67(23.6), 69(22.3), 106(21.6), 39(20.5)
a See Figure 2 for structure formula. b Determined on a Carbowax 20 M silica capillary column. c m/z (relative intensity).

Table 2. 1H and 13C NMR Chemical Shifts of Table 4. 1H and 13C NMR Chemical Shifts of
Compound 5 Compound 7
δ13Ca groupb assignmentc δ1Ha δ13Ca groupb assignmentc δ1Ha
64.00 C C-6 sd 65.13d C C-1 se
54.88 C C-1 s 65.10d C C-13 s
49.00 CH2 C-13 2.82(a)e and 2.75(s) 63.84 C C-8 s
48.25 CH C-8 1.86 60.51 CH C-2 3.01
45.01 CH C-5 2.28 38.55 CH2 C-7 1.70
40.27 CH C-2 1.79 37.55 C C-6 s
37.94 C C-7 s 32.95 CH C-5 1.79
35.50 CH2 C-11 1.77(β) and 1.30(R) 29.92 CH2 C-10 2.13(β) and 1.10(R)
33.50 CH2 C-4 1.57(R) and 1.06(β) 28.37 CH2 C-9 2.02(R) and 1.65(β)
32.10 CH2 C-3 1.90 and 1.13 24.34 CH2 C-4 1.23 and 1.18
25.37 CH2 C-9 1.56 22.47 CH2 C-3 1.99(β) and 1.88(R)
24.08 CH3 C-14 1.04 21.91 CH3 C-14 1.34
23.22 CH2 C-10 1.47(β) and 1.17(R) 20.90 CH3 C-15 1.38
22.25 CH3 C-15 0.68 15.26 CH3 C-11 0.68
19.76 CH3 C-12 0.91 15.04 CH3 C-12 0.90
a In ppm with respect to TMS. b Determined from DEPT a In ppm with respect to TMS. b Determined from DEPT

spectra. c Determined from 2-D measurements. d s, Not deter- spectra. c Determined from 2-D measurements. d Assignment may
mined. e a, anti; s, syn. be reversed. e s, Not determined.

Table 3. 1H and 13C NMR Chemical Shifts of Table 5. 1H-1H Coupling Constantsa of Compounds 5-7
Compound 6
pairs 5 6 7
δ13Ca groupb assignmentc δ1Ha
1-9R 2.0
62.18 CH C-8 3.02 2-3R 3.9
58.89 CH C-2 2.65 2-12 7.1
58.04 C C-7 sd 5-4R 11.2
57.56 C C-3 s 5-4β 6.8
38.49 CH C-10 1.45 5-11 6.9
34.20 CH C-1 2.04 5-13s 0.7
34.13 CH C-6 1.92 8-9R 2.8
28.30 CH C-11 1.68 8-11R 4.6
27.01 CH2 C-9 2.22(R) and 1.36(β) 9R-9β -14.0 -13.0
26.82 CH2 C-4 1.87 and 1.64 9R-10R 2.0 4.0
23.46 CH3 C-15 1.29 9R-10β 14.0
21.84 CH3 C-14 1.32 9β-10R 12.0 3.1
21.57 CH2 C-5 1.62 9β-10β 4.0
21.39 CH3 C-12 0.93 10R-10β -13.2
21.24 CH3 C-13 0.94 11β-11R -11.5
a
11-12 6.5
In ppm with respect to TMS. b Determined from DEPT 11-13 6.5
spectra. c Determined from 2-D measurements. d s, Not deter- 13a-13sb -4.3
mined.
a J in Hz. b a, anti; s, syn.
substituted carbon, and yielded to the corresponding
pure alcohols 8, 9, and 10 (yields >85%). Retention time connectivities is available from the COSY spectrum (Aue
and mass spectral data of these compounds are given et al., 1976; Nagayama et al., 1980). Then, one bond
in Table 1 and NMR data are in Tables 6 and 7. proton-carbon chemical shift correlations were achieved
NMR Results. The strategy used in the assignment by the proton-detected C,H correlation technique (HMQC;
of spectra and determination of the structures requires Bax and Subramanian, 1986). The CHn groups were
the connecting together of individual fragments. As we assigned and assembled from the analysis of long-range
have recently reported (Bombarda et al., 1994; Aycard correlation responses over two or three bonds (2J or 3J
et al., 1993; Faure et al., 1991; Raharivelomanana et al., couplings) with the HMBC sequence (Bax and Sum-
1993, 1994), the molecular framework of this kind of mers, 1986). Finally, the stereochemistry of these rigid
structure can be deduced from the concerted application molecules was unequivocally established from the analy-
of homonuclear and both direct and long-range 1H- sis of the phase-sensitive NOESY diagram (Boden-
detected heteronuclear chemical shift correlation ex- hausen et al., 1984). Preliminary determination of
periments. First, the establishment of the proton structural units followed from the inspection of one-
Sesquiterpenic Epoxides and Alcohols from Vetiver Oil J. Agric. Food Chem., Vol. 44, No. 1, 1996 221

Table 6. 1H and 13C NMR Chemical Shifts of Compounds

8 and 9
8 9
assign- assign-
δ13Ca groupb mentc δ13Ca groupb mentd δ1Ha
76.98 C C-6 76.14 C C-6 se
52.78 C C-1 53.22 CH C-5 1.86
51.84 CH C-5 53.17 C C-1 s
50.79 CH C-8 50.04 CH C-8 1.75
40.37 CH C-2 41.42 C C-7 s
39.86 C C-7 40.15 CH C-2 1.74
36.08 CH2 C-11 36.19 CH2 C-11 1.68 and 1.19
33.18 CH2 C-4 33.19 CH2 C-4 1.64 and 1.04
32.08 CH2 C-3 32.03 CH2 C-3 1.94 and 1.05
27.34 CH3 C-14 26.40 CH3 C-14 0.99 Figure 3. Long-range 13C-1H connectivities for proton methyl
26.31 CH2 C-9 25.55 CH2 C-9 1.55 shifts (7A, 7B) and epoxide resonance (7C), and 1H-1H
23.88 CH3 C-15 23.33 CH2 C-10 1.64 and 1.87 intercoupling network (7D) observed in the case of valencene
23.60 CH2 C-10 23.33 CH3 C-15 0.88 diepoxide 7 (see text).
21.35 CH3 C-13 21.96 CH3 C-13 1.11
19.86 CH3 C-12 19.89 CH3 C-12 0.88
a In ppm with respect to TMS. b Determined from DEPT

spectra. c Determined from 2-D measurements. d Determined by

comparison with 13C chemical shifts of 9 from 2-D measurements.
e s, Not determined.

Table 7. 1H and 13C NMR Chemical Shifts of Compound

10
δ 13Ca groupb assignmentc δ1Ha
72.40 C C-1 sd
65.26 C C-13 s
64.29 C C-8 s
41.68 C C-6 s
35.31 CH2 C-7 1.86 and 1.43
34.80 CH2 C-2 1.74 and 1.37
34.46 CH C-5 1.87
33.57 CH2 C-10 1.63 and 1.27
29.39 CH2 C-4 1.28 and 1.21
24.94 CH2 C-9 2.15 and 1.52
21.97 CH3 C-14 1.35
20.89 CH3 C-15 1.30
20.88 CH2 C-3 1.71 and 1.52
15.42 CH3 C-11 0.73
14.54 CH3 C-12 0.82
a In ppm with respect to TMS. b Determined from DEPT

spectra. c Determined from 2-D measurements. d s, Not deter-

mined.
dimensional spectra. In 5-7 and 10, the occurrence of
an epoxide ring was indicated by 1H and 13C NMR data, Figure 4. Selected through space interaction pathways
and the evidence for quaternary aliphatic alcohols was deduced from the phase sensitive NOESY spectrum of ziza-
clearly established from the 13C NMR chemical shifts. nene and valencene diepoxides 6 and 7.
Further inspection of the remaining 1H resonances these correlations from Drieding model. As for 6,
showed signals for tertiary and secondary methyl groups correlation peaks for 7 between H-15 and H-9β, and
for all compounds. between H-14 and H-7β, indicate that epoxide 8,13 is
The strategy applied in this work is exemplified by R. For some derivatives, the high crowding of methyl-
the structural analysis of valencene diepoxide 7. Utiliz- ene resonances preclude the accurate determination of
ing the HMBC contour plot, structural fragments 7A 1H chemical shifts and proton-proton coupling con-
and 7B (Figure 3), can be determined with the proton stants from one-dimensional measurements. These
methyl shifts. Long-range correlation responses ob- proton resonances, therefore, were assigned from the
served for the epoxide proton CH-2 lead to the substruc- slices of the chemical shift heteronuclear correlation
ture 7C (Figure 3) and unambiguous assignments of diagrams.
methylene carbon C-5, CH2-3, and CH2-10. Finally, Odor Evaluation. These new constituents were
with the proton connectivities obtained from the COSY submitted to olfactory evaluation. A characteristic
spectrum, the structure of 7D (Figure 3) was deter- precious wood- and root-like odor appear to be important
mined, which corresponds to valencene diepoxide 7. The for the head note of this oil and may have valuable
stereochemistry of the two epoxide rings in 6 and 7 and synergistic effects with the other typical vetiver odor
the determination of methyl resonances CH3-14 and compounds.
CH3-15 in 7 were unequivocally established on the basis
of NOE cross-peaks obtained from the phase-sensitive
ACKNOWLEDGMENT
NOESY experiment (Figure 4). For diepoxide 6, cor-
relation peaks between H-9R and H-14, and between We gratefully acknowledge M. How Choong (Mana-
H-9β and H-2, are in agreement with a (7,8)-β and a pany-les-Hauts, Reunion island, France) for providing
(2,3)-R epoxide because only this configuration allows us various Bourbon vetiver essential oil samples.
222 J. Agric. Food Chem., Vol. 44, No. 1, 1996 Bombarda et al.

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