FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fragr. J. 2001; 16: 50–60

Constituents of the acidic part of commercial Brazilian

lantana oil
Peter Weyerstahl,∗ Helga Marschall and Christian Christiansen
Institut für Organische Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany
Received 16 June 2000
Revised 14 August 2000
Accepted 14 August 2000

ABSTRACT: The acidic part of Brazilian lantana oil contains mainly new bisabolene and tricyclic helifolene
derivatives. 3-Formyl-helifolen-12-oic acids 14, 16, 11-formyl-helifolen-15-oic acids 10, 12, 6,10-epoxybisabol-
2- 18, 20, 22, 24, and -3-en-12-oic acids 19, 21, 23, 25, -(26) and ar-curcumen-15-oic acids (27), as well as the
known ar -curcumen-12-oic acid (28) and amorpha-4,9,11-trien-12-oic acid, were characterized as their methyl
esters. The bifunctionalized methyl helifolenoates 10, 12, 14, 16 were reduced with NaBH4 to the corresponding
hydroxy esters 11, 13, 15, 17. Their configuration was clarified by NOED spectra. The helifolen-12- (1a–4a) and
-15-oic acids (5a) are present in the acidic part only as traces. Their spectral data were obtained by isolation from
an autoxidized fraction of the known aldehydes.1 The parent helifolane (syn. khusiane or allo-cedrane) skeleton
8/9 was prepared by stepwise reduction of esters 1b–4b with LiAlH4 and H2 /Pd/C to yield the helifolanols 6
and 7. Treatment of 6, 7 with O-p-tolylchlorothionoformate gave the corresponding thionocarbonates which were
reduced with tris(trimethylsilyl)silane to afford helifolanes 8 and 9. Copyright  2001 John Wiley & Sons, Ltd.
KEY WORDS: Lantana camara L.; Verbenaceae; essential oil; sesquiterpenes; bisabolane; cadinane; helifolane
(syn. allo-cedrane or khusiane); NMR

Introduction amounts of diethyl ether. For numbering, see Schemes

1, 4 and 5.
Recently, we reported on the analysis of the commercial
Brazilian lantana oil,1 but, with the limitation that only
the neutral part was mentioned. We now describe some Separation, Isolation and Identification
new sesquiterpene carboxylic acids isolated from lantana
oil. The acidic part (about 0.7% of the oil, carboxylic
of Compounds
acids) contains mostly derivatives with the bisabolane
and helifolane (syn. allo-cedrane or khusiane) skeleton, Isolation of the Helifolenoic Acids 1a–5a;
also found in the neutral part. Preparation of the Helifolanols 6,7 and
Helifolanes 8, 9

Experimental Helifolenoic Acids 1a–5a

1
H-NMR (CDCl3 ): Bruker AM 400. 13 C-NMR (CDCl3 ):
Bruker AH 270 with DEPT programme. HR–MS: MAT
711, direct inlet (70 eV). GC–MS: Varian 3700 with
a 25 m CP (Chrompack) Sil 5 CB column, combined
with a Varian MAT 44 S, carrier gas He. GC: Packard
439 with a CP Sil 5 CB column (25 m ð 0.25 mm i.d.,
d.f. 0.39 µm), carrier gas N2 , temperature programme,
60 ° C, then 5 ° C/min to 220 ° C. Flash chromatography
(FC) on Merck silica gel (0.040–0.063 mm). Eluants:
light petroleum (boiling range 40–60 ° C) and increasing
*Correspondence to: P. Weyerstahl, Institut für Organische Chemie,
Technische Universität Berlin, Strasse des 17. Juni 135, D-10623
Berlin, Germany.
FC of an autoxidized fraction (2.3 g) of the aldehydes
1–5 (R CHO, see reference 1, neutral part) gave 0.9 of
unchanged aldehydes and 1.3 g of acids. Repeated FC
afforded 2a, 1a, 4a, 3a and 5a (in order of polarity).
Helifolen-12-oic acid (2a, anti–anti–anti): 75 mg,
RI: Sil 5 1745, 3 : 1-mixture of 2a and 1a (1 H-NMR);
m.p. 123 ° C (colourless needles). 1 H-, 13 C-NMR: see
Tables 1 and 2. GC–MS: m/z (%): 234 (4, MC ),189 (1),
161 (5), 145 (7), 133 (4), 122 (17), 121 (32), 120 (13),
119 (100), 105 (16), 93 (23), 92 (10), 91 (20), 87 (10),
79 (11), 77 (13), 55 (10). C15 H22 O2 , calcd. 234.1620,
found 234.1615 (HR–MS).

Copyright  2001 John Wiley & Sons, Ltd.

 ACIDIC PART OF COMMERCIAL LANTANA OIL 51

Table 1. 1 H-NMR data (υ , CDCl3 ) of the helifolen-12-oic acids 1a–4aa and the methyl
helifolen-12-oates 1b - 4b (in parentheses, if different)

H no. 1a (1b) 2a (2b) 3a (3b) 4a (4b)

1 d 6.09 (6.06) 5.81 (5.78) 6.13 (6.10) 6.34 (6.30)
2 d 5.90 (5.87) 5.84 (5.82) 6.02 (5.97) 6.01 (5.96)
4 mc 0.98, 1.97 (1.85) 0.96, 1.95 (1.81) 0.94, 1.68 0.93, 1.67
5 mc 1.25, 1.40 1.18, 1.64 1.00, 1.29 0.92, 1.52
7 ddq 1.72 2.03 1.99 1.77
8 mc 1.25, 1.86 1.17, 2.05 1.34, 1.92 1.22, 2.11
9 mc 1.09, 1.46 1.16, 1.46 1.58 1.55
10 dd 2.46 2.53 1.99 1.98 (2.05)
3-Me s 1.21 (1.12) 1.19 (1.10) 1.15 1.16
7-Me d 1.01 (1.00) 0.93 0.93 (0.92) 1.00
11-Me s 1.05 (1.00) 1.05 (1.00) 1.16 (1.09) 1.17 (1.08)
(11-CO2 Me) s (3.67) (3.67) (3.59) (3.60)
For numbering, see Scheme 1.
a J [Hz] 1, 2 D 8.5; 7, 7-Me D 7; 7, 8 D 6; 7, 80 D 9; 8, 80 D 13; 9, 10 D 8; 90 , 10 D 12.

Helifolen-12-oic acid (1a, syn–anti–anti): 17 mg, Methyl Helifolenoates 1b–5b

RI: Sil 5 1745, 2 : 1 mixture of 1a and 2a (1 H-NMR);
m.p. 137 ° C (colourless needles). 1 H-, 13 C-NMR: see Treatment of the acids 1a–5a with CH2 N2 as usual
Tables 1 and 2. GC–MS: identical with that of 2a. yielded the methyl esters 1b–5b.

Helifolen-12-oic acid (4a, syn–syn–syn): 10 mg, RI: Methyl Helifolen-12-oates 1b–4b

Sil 5 1780, 4 : 2 : 1 mixture of 4a, 3a and 5a (1 H-NMR);
m.p. 108 ° C (colourless needles). 1 H-, 13 C-NMR: see
Tables 1 and 2. GC–MS: identical with that of 2a.
Helifolen-12-oic acid (3a, anti–syn–syn): 25 mg, RI:
Sil 5 1780, 2 : 1 mixture of 3a and 4a (1 H-NMR); m.p.
95 ° C (colourless needles). 1 H-, 13 C-NMR: see Tables 1
and 2. GC–MS: identical with that of 2a.
Helifolen-15-oic acid (5a): Ca. 15% (1 H-NMR)
together with 3a (30%) and 4a (55%). 1 H-NMR: υ 0.82,
1.19 (2 s, 11-Me2 ), 1.00 (d, J D 7 Hz, 7-Me), 6.09, 6.54
(2 d, J D 8.5 Hz, 1-, 2-H).
Table 2. 13 C-NMR data (υ, CDCl3 ) of the helifolen-12-oic
acids 1a–4aa,b (for numbering, see Scheme 1)
FC gave (in order of polarity) 2b, 1b, 4b, 3b and 5b.
2b (anti–anti–anti) and 1b (syn–anti–anti): 2 : 1
mixture; oily; RI: Sil 5 1655 (2b), 1662 (1b), wax 2050
(2b), 2060 (1b). 1 H-, 13 C-NMR: see Tables 1 and 2.
GC–MS (1b D 2b): m/z (%) 248 (2, MC ), 216 (5), 201
(1), 189 (3), 161 (4), 158 (8), 145 (7), 135 (4), 122
(9), 121 (22), 120 (11), 119 (100), 105 (10), 101 (11),
93 (17), 91 (12), 88 (7), 81 (7), 79 (8), 77 (8), 55 (7).
C16 H24 O2 , calcd. 248.1776, found 248.1773 (HR–MS).
3b (anti–syn–syn) and 4b (syn–syn–syn): 5 : 3-
mixture; oily; RI: Sil 5 1672 (4b), 1680 (3b), wax 2127
(4b), 2140 (3b). 1 H-, 13 C-NMR: see Tables 1 and 2.
GC–MS: identical with that of 1b/2b.

C no. 1a 2a 3a 4a Methyl helifolen-15-oate (5b): GC: 15%, together

with 3b (23%) and 4b (55%); oily; RI: Sil 5 1688, wax
1 d 131.6 137.3 135.3 133.3
2 d 138.5 140.1 139.8 139.1 2132. 1 H-NMR: υ 0.75, 1.11 (2 s, 11-Me2 ), 0.99 (d,
3 s 41.9 41.9 40.6 40.8 J D 7 Hz, 7-Me), 6.06, 6.54 (2 d, J D 8.5 Hz, 1-, 2-H),
4 t 31.0 30.8 32.0 32.5 3.71 (s, CO2 Me). GC–MS: m/z (%) 248 (8, MC ), 233
5 t 31.2 27.9 17.8 26.9
6 s 49.5 48.3 48.1 47.4 (2), 217 (3), 205 (16), 189 (12), 164 (25), 163 (82), 145
7 d 39.2 38.9 38.5 36.9 (13), 137 ( 28), 133 (23), 131 (13), 119 (41), 109 (26),
8 t 31.9 33.8 31.1 33.6 105 (100), 93 (22), 91 (74), 83 (28), 82 (76), 79 (31),
9 t 24.9 27.2 22.5 23.1
10 d 52.8 50.2 53.9 51.7 77 (30), 69 (45), 67 (29), 59 (30), 55 (89); the GC–MS
11 s 52.7 52.4 48.7 48.5 is nearly identical with that of 26.
11-CO2 H s 183.8 184.5 183.2 184.0
11-Me q 18.3 18.1 16.0 16.0 Preparation of the Helifolanols 6, 7 and
3-Me q 20.8 20.7 20.6 20.6
7-Me q 14.7 18.2 15.0 19.8 Helifolanes 8, 9

LiAlH4 reduction (1 h, 25 ° C) of a 1 : 2-mixture (80 mg)

aWith 1 H,13 C correlation.
b
The values are nearly the same for the methyl helifolen-12-oates 1b–4b.
11-CO2 Me (instead of CO2 H): 1b, 2b 177.9, s, 51.4, q; 3b, 4b 178.4, s, of 1b and 2b or 3b and 4b and consecutive hydrogena-
51.5, q. tion (2 h) of the helifolenols (1/2 and 3/4, R D CH2 OH;

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
52 P. WEYERSTAHL, H. MARSCHALL AND C. CHRISTIANSEN

for data see reference 1) on Pd/C in MeOH/EtOH yielded
a 1 : 2 mixture (75 mg) of 6 and 7.
Helifolan-12-ol (6, anti) and 7-epi-Helifolan-12-ol
(7, syn): Oily; GC, 37% of 6, 60% of 7; RI: Sil 5 1697
(7), 1710 (6); wax 2446 (7), 2461 (6). 1 H-NMR (6/7):
υ 0.72/0.71 (s, 3-Me), 0.76/0.79 (d, J D 7 Hz, 7-Me),
0.93/0.94 (s, 11-Me), 1.05, 1.96 (8-H2 , 7), 1.43/1.43 (mc ,
7-H), 1.48/1.43 (dd, J D 11, 11 Hz, 10-H), 1.56/1.46,
1.52 (mc , 9-H2 ), 3.42, 3.54/3.43, 3.52 (2 d, J D 10 Hz,
11-CH2 OH). 13 C-NMR: see Table 3. GC–MS (6 D 7):
m/z (%) 222 (0.5, MC ), 204 (1), 191 (50), 135 (23), 121
(20), 109 (28), 107 (26), 105 (18), 95 (100), 93 (37), 91
(28), 81 (95), 79 (34), 77 (22), 69 (22), 67 (28), 55 (32).
C15 H26 O, calcd. 222.1984, found 222.1978 (HR–MS).
Analogously, a 3 : 2 mixture of 6 and 7 was pre-
pared from a 3 : 2 mixture of 3b and 4b as described
above. Analogously, a 1 : 1 : 2 : 1 mixture of 1b/2b/3b/4b
yielded a 3 : 2 mixture of 6 and 7.
According to reference 3, a 2 : 1 mixture (50 mg) of 6
and 7 was treated with O-p-tolylthionoformate (0.04 ml)
and DMAP (90 mg) in dry CH2 Cl2 (5 ml) overnight.
After the usual work-up, the mixture of thionocarbon-
ates (50 mg) was dissolved in dry benzene (5 ml) and
tris(trimethylsilyl)silane in excess (1.5-fold) and AIBN
(0.5-fold) was added. The mixture was heated under N2
for 8 h to 80 ° C. Work-up, as described in reference 2,
afforded a 2 : 1 mixture of 8 and 9 (10 mg).
Helifolane (8, anti) and 7-epi-Helifolane (syn.
khusiane or ent-allo-cedrane; 9, syn): Oily; GC,
60% of 8, 35% of 9. RI: Sil 5 1430 (9), 1440 (8); wax
1606 (9), 1618 (8). 1 H-NMR (8/9): υ 0.69/0.68 (s, 3-Me),
0.75/0.78 (d, J D 7 Hz, 7-Me), 0.83, 0.87/0.84, 0.86 (s,
11-Me2 ), 1.14/0.98 (mc , 8-H), 1.38/1.31 (dd, J D 11,
11 Hz, 10-H), 1.55/1.35, 1.51 (mc , 9-H2 ), 1.43/1.43 (mc ,
7-H), 1.79/1.93 (mc , 80 -H); reference 4: 1 H-NMR of
khusiane 9 (60 MHz, CCl4 ) υ 0.69 (s, Me), 0.75 (d,
J D 6 Hz, Me), 0.86 (s, 2 Me). 13 C-NMR: see Table 3.
8: GC–MS: m/z (%) 206 (13), MC ), 191 (4), 163 (71),
136 (14), 121 (50), 107 (54), 95 (74), 93 (61), 82 (100),
81 (86), 79 (40), 69 (40), 67 (38), 55 (36). 9: GC–MS:
m/z (%) 206 (10, MC ), 191 (4), 163 (50), 136 (24),
123 (24), 121 (42), 107 (42), 95 (73), 93 (61), 82 (95),
81 (100), 79 (42), 69 (48), 67 (41), 55 (38); in good
agreement with the data given in reference 4.
Isolation of Formyl Helifolenoic Acid Methyl
Esters 10, 12, 14, 16, 6,12-Epoxybisabolenoic Acid
Methyl Esters 18–25, Curcumenoic Acid Methyl
Esters 26–28 and Pyrazoline 30
As described in reference 1, 1.7 g of acidic material
was isolated from 285 g of the oil. Treatment with an
ethereal CH2 N2 solution as usual furnished a mixture of
the corresponding methyl esters, M.
FC of the mixture of methyl esters M (0.5 g) yielded
1. 75 mg (mainly 20, 24, 26), 2. 40 mg of 18 (mainly),
3. 30 mg of 14, 16, 19, 4. 45 mg of 10, 12, 5. 35 mg,
not investigated, 6. 90 mg of 30 (mainly).
Re-FC of fraction 1 gave fraction 1.1., 6 mg, 27; 1.2.,
7 mg, not investigated; 1.3., 10 mg, 26; 1.4., 7 mg, 28;
1.5., 30 mg, 20 (mainly), 21, 22, 23; 1.6., 15 mg, 24
(mainly), 18, 20.
Re-FC on florisil of fraction 1.5. gave fraction 1.5.1.,
7 mg, 21 (mainly), 22, 23; fraction 1.5.2., 9 mg, 20
(mainly), 18, 24; fraction 1.5.3., 3 mg, 20 (mainly), 24.
Methyl formyl-helifolenoates 10, 12, 14, 16
Methyl syn-(10) and anti-11-Formyl-helifolen-15-
oate (12): Oily; GC: 56 : 44 mixture of 10 and 12. RI:
Sil 5 1850 (10), 1845 (12). 1 H-, 13 C-NMR: see Tables 4
and 5. GC–MS (10 D 12): m/z (%) 234 (6, MC - CO),
230 (7), 202 (16), 163 (18), 147 (13), 145 (68), 133 (18),
131 (27), 119 (35), 107 (24), 105 (100), 93 (26), 91 (69),
81 (24), 79 (38), 77 (40), 59 (53), 55 (44), 53 (26).

Table 3. 13 C-NMR data (υ , CDCl3 ) of the helifolanols 6, 7 and

the helifolanes 8, 9 (for numbering, see Scheme 1)

C no. 6 anti 8 anti 7 syn 9 syn

1 t 32.7 33.0 29.0 29.3
2 t 31.8 31.8 31.0 31.3
3 s 34.0 34.4 34.1 34.4
4 t 31.7 31.2 32.7 32.2
5 t 20.1 20.3 31.7 31.6
6 s 40.7 42.7 40.5 41.1
7 d 42.4 42.6 39.7 40.2
8 t 32.2 32.1 35.0 35.5
9 t 23.8 22.2 25.7 24.1
10 d 50.9 55.1 49.6 54.1
11 s 42.6 35.5 41.3 35.5
11-R t 70.8 q 27.1 t 70.7 q 26.7
11-Me q 15.7 21.2 15.4 20.7
7-Me q 14.2 14.3 17.6 17.5
3-Me q 22.0 21.4 21.8 21.3

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
 ACIDIC PART OF COMMERCIAL LANTANA OIL 53

Table 4. Typical 1 H-NMR data (υ , CDCl3 ) of the functionalized helifolenoates 10–17 (for numbering see Scheme 1)
H no. 10 anti 11 anti 12 syn 13 syn 14 anti 15 anti 16 syn 17 syn
1 d 6.21 6.11 5.96 5.87 6.22 6.16 5.88 5.91
2 d 6.61 6.54 6.51 6.43 6.29 5.88 6.19 5.80
7 qdd 1.78 1.68 2.11 2.04 1.77 1.72 2.09 2.04
10 dd 1.98 2.06 2.46 2.36 2.50 2.42
11-R s 9.75 3.40 s 9.75 3.42
3.82 3.79
11-Me s 0.87 0.87 0.89 0.88 1.09 1.06 1.11 1.06
7-Me d 1.04 1.00 0.95 0.90 1.02 1.01 0.95 0.94
3-R s 9.95 3.70 s 9.94 3.70
3.99 3.95
CO2 Me s 3.72 3.76 3.72 3.75 3.71 3.69 3.71 3.69
Additional υ values: 4-H2 10 2.27, 1.31; 12 2.25, 1.64.
5-H2 10 1.35, 1.41; 12 1.22, 1.35.
8-H2 10 1.28, 2.09; 12 1.21, 2.08;
9-H2 10 1.09, 1.35; 12 1.35.
10–16: J [Hz]: 1, 2 D 8.5; 4, 40 D 5, 50 D 11; 40 , 5 D 4, 50 D 10; 4, 5 D 40 , 50 D 4;
7, 7-Me D 7; 7, 8 D 9; 7, 80 D 6; 8, 80 D 13; 8, 9 D 12; 80 , 9 D 80 , 90 D 9;
8, 90 D 4; 9, 10 D 11.5; 90 , 10 D 8.5.
different J for 12, 16: 7, 8 D 7; 7, 80 D 5; 8, 80 D 14; 8, 9 D 9; 8, 90 D 2; 9, 10 D 12; 90 , 10 D 7.
11, 13, 15, 17: R D CH2 OH; J [Hz]: 12, 120 D 11.5.

Table 5. 13 C-NMR data (υ, CDCl3 ) of the functionalized methyl helifolenoates 10–17a (for numbering, see
Scheme 1)

C no. 10 anti 11 anti 12 syn 13 syn 14 anti 15 anti 16 syn 17 syn

1 d 132.3 131.1 140.7 139.7 129.6 132.3 141.4 140.9
2 d 132.3 133.8 131.1 132.7 132.9 134.0 128.5 132.8
3 s 53.3 52.7 53.3b 52.6 55.3 47.2 55.3 47.3
4 t 27.1 26.3 26.3 25.9 24.5 25.5 24.2 25.2
5 t 29.3 29.8 26.4 27.1 29.7 30.5 26.7 27.5
6 s 50.0 50.0 49.1 48.9 50.6 49.7 49.6 48.5
7 d 39.1 39.3 38.8 38.9 39.1 39.2 38.6 38.9
8 t 31.7 31.9 33.6 33.9 31.7 31.8 33.6 33.8
9 t 24.1 24.8 26.8 27.0 24.4 24.7 26.7 27.0
10 d 49.8 54.6 47.2 51.6 51.6 53.5 49.2 51.1
11 s 54.3 47.3 53.8 46.9 54.4 52.1 54.0 51.6
11-R d 203.7 t 70.4 d 203.7 t 70.2 s 177.4 s 179.6 s 177.4 s 179.5
11-Me q 16.3 18.6 16.2 18.4 19.9 18.9 19.6 18.6
7-Me q 14.6 14.6 18.2 18.1 14.6 14.7 18.2 18.2
3-R s 174.3 s 177.4 s 174.3 s 177.4 d 204.1 t 65.6 d 204.0 t 65.6
CO2 Me q 52.1 52.1 52.1 52.1 52.2 52.1 52.2 52.1
a
10, 12, 14, 16: With NOED and 1 H,13 C correlation.
b
Estimated value, not observed due to low concentration.

Methyl syn-(14) and anti-3-Formyl-helifolen-12- Methyl syn- (11) and anti-11-Hydroxymethyl-heli-

oate (16): Oily; 30 : 25 : 40 mixture of 19, 16 and
14. RI: Sil 5 1793 (14), 1788 (16). 1 H-, 13 C-NMR:
see Tables 4 and 5. GC–MS (14 D 16): m/z (%) 262
(1, MC ), 234 (2), 230 (3), 202 (8), 175 (10), 147
(43), 144 (29), 131 (24), 119 (23), 114 (78), 107
(59), 105 (100), 101 (18), 91 (57), 88 (29), 82 (19),
81 (15), 79 (51), 77 (36), 65 (19), 59 (19), 55 (36),
53 (24). C16 H22 O3 calcd. 262.1569, found 262.1566
(HR–MS).
NaBH4 Reduction of 10/12 and 14/16
Usual reduction of the mixtures of 10/12 and 14/16 with
NaBH4 in MeOH furnished after work-up and FC the
hydroxy esters 11/13 and 15/17.
folen-15-oate (13): The 56 : 44 mixture (20 mg) of
10 and 12 gave an oily 3 : 2 mixture (1 H-NMR; 15 mg)
of 11 and 13. RI: Sil 5 1922 (11, 13). 1 H-, 13 C-NMR:
see Tables 4 and 5. GC–MS (11Y13): m/z (%) 246 (2,
MC –H2 O), 232 (7), 217 (2), 204 (11), 189 (8), 187 (13),
176 (94), 164 (24), 163 (38), 159 (16), 145 (47), 137
(23), 131 (70), 121 (24), 119 (42), 117 (20), 115 (18),
107 (24), 105 (100), 96 (18), 94 (18), 93 (43), 91 (90),
83 (23), 81 (45), 79 (46), 77 (40), 68 (16), 67 (21), 65
(21), 59 (47), 55 (62), 53 (29).
Methyl syn- (15) and anti-3-Hydroxymethyl-heli-
folen-12-oate (17): The 30 : 25 : 40 mixture (20 mg)
of 19, 16 and 14 gave an oily mixture (18 mg) of 19,
17 and 15, which was separated by FC. 19 (3 mg, see

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
54 P. WEYERSTAHL, H. MARSCHALL AND C. CHRISTIANSEN

below) eluated as first fraction, a 1 : 2 mixture (13 mg) Methyl 11-epi-6,10-epoxybisabol-2-en-12-oate

of 17 and 15 was obtained as second fraction. RI: Sil 5
1905 (15), 1894 (17). 1 H-, 13 C-NMR: see Tables 4 and
5. GC–MS (15 D 17): m/z (%) 246 (0.5, MC –H2 O),
232 (6), 217 (3), 204 (6), 187 (16), 186 (11), 159
(60), 158 (28), 152 (34), 145 (49), 131 (40), 127 (28),
120 (35), 119 (82), 118 (38), 117 (30), 115 (25), 114
(28), 107 (28), 105 (84), 101 (26), 95 (28), 91 (100),
81 (46), 79 (66), 77 (39), 67 (39), 65 (28), 55 (60),
53 (33).
(20 D C): 3 mg, oily; RI: Sil 5 1763; GC: 85%, mixture
with 5% of G (1 H-NMR). 1 H-, 13 C-NMR: see Tables 6
and 7. GC–MS: m/z (%) 266 (3, MC ), 248 (13), 235
(1), 198 (8), 166 (3), 161 (17), 121 (29), 119 (52), 111
(54), 110 (63), 105 (26), 95 (40), 93 (49), 91 (28), 88
(61), 82 (26), 81 (35), 79 (29), 69 (29), 68 (53), 67 (51),
59 (37), 57 (29), 55 (100), 53 (29); nearly identical with
that of F. C16 H26 O3 , calcd. 266.1882, found 266.1880
(HR–MS).

Methyl 6,10-Epoxybisabolen-12-oates Methyl 11-epi-6,10-epoxybisabol-3-en-12-oate

(18–25 D A–H)
Methyl 6,10-epoxybisabol-2-en-12-oate (18 D A):
25 mg, oily; RI: Sil 5 1746; GC, 70%; together with 12%
of C C G and 15% of F. 1 H-, 13 C-NMR: see Tables 6
and 7. GC–MS: m/z (%) 266 (6, MC ), 248 (22), 235
(3), 198 (12), 166 (6), 161 (32), 121 (43), 119 (100,
Me–C6 H4 –CHMežC ), 111 (66, Me–C6 H7 OHžC ), 110
(70, Me–C6 H7 Ož ), 105 (39), 95 (49), 93 (63), 92 (32),
91 (31), 88 (90, Me–CH2 –CO2 Mež ), 82 (32), 81 (43),
79 (30), 69 (35), 68 (58), 67 (52), 59 (41), 57 (29), 55
(95), 53 (30).
Methyl 6,10-epoxybisabol-3-en-12-oate (19 D B):
3 mg, oily; RI: Sil 5 1735; GC: 80%, mixture with
15% of 25 D H). 1 H-, 13 C-NMR: see Tables 6 and 7.
GC–MS: m/z (%) 266 (5, MC ), 248 (14), 235 (1), 198
(18), 166 (8), 161 (14), 121 (40), 119 (32), 111 (91),
110 (57), 105 (20), 95 (43), 93 (35), 91 (26), 88 (53),
81 (34), 79 (26), 69 (27), 68 (42), 67 (48), 59 (32), 57
(28), 55 (100), 53 (31).
(21 D D): 7 mg, oily; 4 : 2 : 2 : 1 mixture with C, E and F
(1 H-NMR). RI: Sil 5 1739. 1 H-, 13 C-NMR: see Tables 6
and 7. GC–MS: m/z (%) 266 (2, MC ), 248 (6), 235
(0.6), 198 (14), 166 (6), 161 (10), 121 (31), 119 (24),
111 (100), 110 (60), 109 (26), 105 (18), 95 (37), 93 (29),
91 (19), 88 (62), 81 (27), 79 (19), 69 (23), 68 (38), 67
(35), 59 (28), 57 (18), 55 (77), 53 (23); nearly identical
with that of E.
Methyl 7,11-di-epi-6,10-epoxybisabol-2-en-12-oate
(22 D E): 20% in the mixture with D (see above). RI:
Sil 5 1771. 1 H-NMR: see Table 6. GC–MS: m/z (%)
266 (5, MC ), 248 (11), 235 (0.5), 198 (24), 166 (7), 161
(10), 121 (21), 119 (20), 111 (100), 110 (55), 109 (21),
105 (15), 95 (35), 93 (24), 88 (48), 81 (26), 69 (20), 68
(38), 67 (35), 59 (26), 57 (26), 55 (74), 53 (21); nearly
identical with that of D.
Methyl 7,11-di-epi-6,10-epoxybisabol-3-en-12-oate
(23 D F): 15% in the mixture with A (70%, see above).
RI: Sil 5 1774. 1 H-, 13 C-NMR: see Tables 6 and 7.
GC–MS: m/z (%) 266 (2, MC ), 248 (7), 235 (0.5), 198

Table 6. 1 H-NMR data (υ, CDCl3 ) of the 6,10-epoxybisabolenoates 18–21 (A–D) and typical data of 22–25 (E–H)a
(for numbering, see Scheme 4)

H no. 18 (A) 20 (C) 22 (E) 24 (G) H no. 19 (B) 21 (D) 23 (F) 25 (H)
1ax 2.29 2.36 2.32 2.35 5ax 1.81 1.83
1eq 1.70 1.70 2.20 5eq 2.30 2.33
2 ddq 5.16 5.24 5.20 5.18 4 ddq 5.19 5.20 5.19 5.19
4ax 2.02 2.00 2ax 1.68 1.74
4eq 1.70 1.78 2eq 1.74 1.80
5ax 1.30 1.34 1ax 1.78 1.82
5eq 2.01 2.06 1eq 1.46 1.44
7 ddq 1.52 1.50 1.54 1.44 1.52 1.48 1.42
8ax 1.45 1.44 1.32 1.34
8eq 1.59 1.60 1.56 1.54
9ax 1.16 1.27 1.19 1.30
9eq 1.70 1.52 1.72 1.54
10 ddd 3.53 3.52 3.65 3.67 3.54 3.57 3.70 3.66
11 dq 2.39 2.40 2.40 2.42 2.41 2.40 2.40 2.44
11-CO2 Me 3.59 3.66 3.64 3.60 3.58 3.62 3.62 3.63
11-Me d 1.065 1.19 1.16 1.07 1.05 1.10 1.10 1.05
7-Me d 0.795 0.81 0.995 0.99 0.81 0.815 0.99 0.99
3-Me dd 1.62 1.64 1.64 1.63 1.62 1.64 1.64 1.62
a
J [Hz]: 18, 20: 1ax , 1eq D 17; 1eq , 2 D 3; 1ax , 2 D 2; 1ax , 3-Me D 2; 2, 3-Me D 1; 4ax , 4eq D 15; 4ax , 5ax D 13; 4ax , 5eq D 4; 4eq , 5ax D 6; 4eq ,5eq D 2; 7,
7-Me D 7; 7ax , 8ax D 8ax , 8eq D 8ax , 9ax D 12; 7ax , 8eq D 8eq , 9eq D 3; 8ax , 9eq D 8eq , 9ax D 4; 9ax , 10ax D 11; 9eq , 10ax D 2; 10ax , 11 D 8; 11, 11-Me D 7.
19, 21: J of 10-, 11-H and of 3-Me, 7-Me and 11-Me are identical with those of 18, 20.
22 –24: 10-H: ddd, J D 11, 8, 2 Hz.

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
 ACIDIC PART OF COMMERCIAL LANTANA OIL 55

Table 7. 13 C-NMR data (υ, CDCl3 ) of the 6,10-epoxybisabolenoates 18–21 (A–D),

23 (F) and 24 (G)a (for numbering, see Scheme 4)

C-no. 18(A) 19(B) 20(C) 21(D) 24(G) 23(F)

1 t 36.6 33.4 36.9 33.7 36.9 31.9
2 d 117.7 26.8 118.1 27.2 117.9 26.7
3 s 133.1 133.7 133.1 134.2 132.0 134.0
4 t 25.6 116.9 25.9 116.6 26.6 118.0
5 t 21.1 23.0 21.0 23.1 21.2 23.7
6 s 74.8 74.6 74.9 74.6 73.0 73.6
7 d 37.9 40.1 38.0 40.2 33.5 33.0
8 t 28.0 28.1 28.2 28.3 27.9 27.9
9 t 29.3 29.7 30.3 30.3 29.7 30.1
10 d 72.2 71.8 70.9 70.4 72.0 70.9
11 d 46.0 46.5 46.2 45.7 46.2 45.7
11-CO2 Me s 176.4 175.9 175.7 175.6 n.o. 175.5
q 51.2 51.3 51.5 51.4 51.5 51.4
11-Me q 13.2 13.2 13.6 12.8 13.0 12.8
7-Me q 17.4 17.3 17.5 17.2 13.9 14.1
3-Me q 23.3 23.4 23.3 23.2 22.9 23.0
a18–20: With NOED and1 H,13 C correlation.
n.o.: not observed due to too low intensity.

(9), 166 (3), 161 (12), 121 (22), 119 (45), 111 (62), 110
(70), 105 (22), 95 (41), 93 (38), 91 (23), 88 (60), 82
(28), 81 (33), 79 (24), 69 (28), 68 (57), 67 (45), 59 (38),
57 (34), 55 (100), 53 (28); nearly identical with that
of C.
Methyl 7-epi-6,10-epoxybisabol-2-en-12-oate
(24 D G): 9 mg, oily; 3 : 4 : 2 mixture (1 H-NMR) with C
and A. RI: Sil 5 1763. 1 H-, 13 C-NMR: see Tables 6 and
7. GC–MS: same RI as C, therefore not determinable.
Methyl 7-epi-6,10-epoxybisabol-3-en-12-oate
(25 D H): 15% in the mixture with B (see above). RI:
Sil 5 1763. 1 H-NMR: see Table 6. GC–MS: m/z (%)
266 (4, MC ), 248 (12), 235 (0.5), 198 (20), 166 (6), 161
(10), 121 (18), 119 (70), 111 (100), 110 (54), 109 (23),
105 (23), 95 (37), 93 (27), 91 (33), 88 (48), 81 (29), 79
(20), 69 (23), 68 (36), 67 (38), 59 (30), 57 (29), 55 (87),
53 (29).
Methyl Curcumenoates 26–28
Methyl ar-curcumen-15-oate (27): Oily, 6 mg, from
fraction 1.1.; RI: Sil 5 1820, wax 2420; GC: 42%. 1 H-
NMR: υ 1.25 (d, J D 7 Hz, 7-Me), 1.50, 1.66 (2 s, br.,
11-Me2 ), 1.63 (mc , 8-H2 ), 1.86, 2.04 (2 mc , 9-H2 ), 2.77
(qt, J D 7, 7 Hz, 7-H), 3.90 (s, CO2 Me), 5.07 (t, br.,
J D 7 Hz, 10-H), 7.24, 7.96 (2 d, br., J D 8 Hz, 4 H-
Ar). GC–MS (MAT): m/z (%) 246 (12, MC ), 215 (6),
187 (5), 176 (100), 164 (32), 163 (53), 149 (20), 145
(36), 131 (52), 105 (70), 103 (20), 91 (37), 83 (39), 77
(29), 69 (42), 59 (40), 55 (93).
Methyl
-curcumen-15-oate (26): Oily, 8 mg from
fraction 1.3.; RI: Sil 5 1850, wax 2410. GC: 68%. [˛]D -
50.1 ° (c 10, CHCl3 ). 1 H-NMR: υ 1.05 (d, J D 7 Hz,
7-Me), 1.35, 1.46 (2 td, J D 7.5, 7 Hz, 8-H2 ), 1.57, 1.67
(2 s, br., 11-Me2 ), 1.91 (td, J D 7.5, 7 Hz, 9-H2 ), 2.15
(td, J D 9, 3 Hz, 5-H2 ), 2.27 (qt, J D 7, 7 Hz, 7-H),
2.44 (td, J D 9, 1 Hz, 4-H2 ), 3.75 (s, CO2 Me), 5.08 (t,
br., J D 7 Hz, 10-H), 5.82, 7.00 (2 d, br., J D 5 Hz,
1-, 2-H). 13 C-NMR: υ 17.7, 25.7 (2 q, 11-Me2 ), 19.1
(q, 7-Me), 21.8 (t, C-5), 24.4 (t, C-4), 26.0 (t, C-9),
34.9 (t, C-8), 40.6 (d, C-7), 118.2 (d, C-1), 124.3 (d,
C-10), 124.8 (s, C-3), 131.6 (s, C-11), 134.5 (d, C-2),
153.0 (s, C-6); CO2 Me: 168.0 (s), 51.5 (q). GC–MS
(MAT): m/z (%) 248 (10, MC ), 205 (9), 189 (7), 176
(12), 164 (17), 163 (57), 145 (17), 137 ( 28), 133 (20),
131 (17), 119 (27), 109 (18), 105 (95), 93 (18), 91 (60),
83 (22), 82 (49), 79 (25), 77 (30), 69 (47), 67 (28),
59 (39), 55 (100); the GC–MS is nearly identical with
that of 5b. C16 H24 O2 , calcd. 248.1776, found 248.1769
(HR–MS).
Methyl ar-curcumen-12-oate (28): Oily, 7 mg, iso-
lated from fraction 1.4.; GC: 20%, together with 60%
of 26. RI: Sil 5 1810, wax 2450. 1 H-NMR: υ 1.24
(d, J D 7 Hz, 7-Me), 1.68 (mc , 8-H2 ), 1.73 (s, br., 11-
Me), 2.05 (mc , 9-H2 ), 2.32 (s, Me–Ar), 2.67 (qt, J D 7,
7 Hz, 7-H), 3.72 (s, CO2 Me), 6.73 (tq, J D 7, 1 Hz,
10-H), 7.06, 7.11 (AB, br., J D 8 Hz, 4 H–Ar); in
good agreement with the values given in reference 5.
GC–MS: in agreement with the values given in refer-
ence 5.
Pyrazoline 30: diazomethane adduct of amorpha-
4,9,11-trien-12-carboxylic acid (29): 30 mg of oily
30 were isolated from fraction 6. RI: Sil 5 1875. 1 H-
NMR (with NOED): υ 1.40 (ddd, br., J D 14, 6, 4 Hz,
8-H), 1.61 (s, br., 4-Me), 1.64 (d, br., J D 1 Hz, 10-
Me), 1.64 (mc , 2-, 3-H), 1.74 (mc , 13-H), 1.80 (mc , 3-,
8-H0 ), 1.99 (d, br., J D 12 Hz, 2-H0 ), 2.26 (ddd, J D 13,
10, 5 Hz, 130 -H), 2.51 (mc ,1-H), 2.54 (mc , 6-H), 3.06
(ddd, J D 12, 4, 3 Hz, 7-H), 3.79 (s, CO2 Me), 4.48 (ddd,

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
56 P. WEYERSTAHL, H. MARSCHALL AND C. CHRISTIANSEN
J D 18, 10, 7 Hz) and 4.65 (ddd, J D 18, 10, 5 Hz,
16-H2 ), 5.05 (s, br., 5-H), 5.39 (ddq, br., J D 6, 1.5,
1 Hz, 9-H). 13 C-NMR (with COSY): υ 20.5 (q, 10-Me),
22.3 (t, C-13), 22.7 (t, C-8), 24.1 (q, 4-Me), 24.8 (t,
C-2), 36.7 (d, C-6), 39.0 (d, C-1), 42.9 (d, C-7), 78.6
(t, C-16), 102.8 (s, C-11), 118.5 (d, C-5), 122.4 (d, C-
9), 133.7 (s, C-10), 137.5 (s, C-4); CO2 Me: 170.7 (s),
52.7 (q). GC–MS (MAT): m/z (%) 260 (24, MC –N2 ),
245 (10), 228 (12), 213 (8), 185 (18), 160 (20), 145
(42), 134 (36), 131 (30), 119 (56), 115 (30), 105 (78),
100 (31), 93 (36), 91 (100), 81 (30), 79 (72), 77 (68),
69 (40), 67 (28), 65 (29), 59 (30), 55 (54), 53 (40).
C17 H24 O2 (M–N2 ), calcd. 260.1776, found 260.1775
(HR–MS).
Preparation of 31 and 32
ar-Curcumen-15-ol (31): LiAlH4 reduction of 27
yielded oily ar-curcumen-15-ol (31). Alternatively, 31
was obtained by NaBH4 reduction of ar-curcumen-15-al
(33).1 RI: Sil 5 1705. 1 H-NMR: υ 1.23 (d, J D 7 Hz,
7-Me), 1.52, 1.67 (2 s, br., 11-Me2 ), 1.58, 1.63 (ABtd,
J D 15, 7, 7 Hz, 8-H2 ), 1.84, 1.90 (ABtd, J D 15, 7,
7.5 Hz, 9-H2 ), 2.70 (qt, J D 7, 7 Hz, 7-H), 4.66 (s, br.,
Scheme 1
Copyright  2001 John Wiley & Sons, Ltd.
CH2 OH), 5.08 (t, br., J D 7.5 Hz, 10-H), 7.18, 7.30 (2 d,
br., J D 8 Hz, 4 H–Ar). 13 C-NMR: υ 17.7, 25.7 (2 q,
11-Me2 ), 22.4 (q, 7-Me), 26.1 (t, C-9), 38.4 (t, C-8),
39.2 (d, C-7), 65.3 (t, C-15), 124.4 (d, C-10), 127.2,
127.3 (2 d, C-1, -2, -4, -5), 131.5 (s, C-11), 138.3 (s,
C-6), 147.3 (s, C-3). GC–MS (MAT): m/z (%) 218 (14,
MC ), 187 (4), 173 (1), 148 (68), 135 (65), 133 (18),
131 (63), 121 (14), 119 (15), 117 (22), 107 (19), 106
(31), 105 (84), 91 (54), 83 (28), 79 (37), 77 (29), 69
(35), 67 (14), 55 (100). C15 H22 O, calcd. 218.1671, found
218.1641 (HR–MS).
15-Acetoxy-ar-curcumene (32): Treatment of 31 with
acetic anhydride and DMAP in CH2 Cl2 as usual gave
oily acetate 32. RI: Sil 5 1840. 1 H-NMR: υ 1.23 (d,
J D 7 Hz, 7-Me), 1.52, 1.67 (2 s, br., 11-Me2 ), 1.57,
1.62 (ABtd, J D 15, 7, 7 Hz, 8-H2 ), 1.85, 1.90 (ABtd,
J D 15, 7, 7.5 Hz, 9-H2 ), 2.10 (s, OCOMe), 2.70 (qt,
J D 7, 7 Hz, 7-H), 5.08 (s, CH2 OAc), 5.08 (t, br.,
J D 7.5 Hz, 10-H), 7.18, 7.28 (2 d, br., J D 8 Hz, 4
H–Ar). 13 C-NMR: υ 17.7, 25.7 (2 q, 11-Me2 ), 21.1 (q,
MeCOO), 22.3 (q, 7-Me), 26.1 (t, C-9), 38.3 (t, C-8),
39.2 (d, C-7), 66.3 (t, C-15), 124.4 (d, C-10), 127.3,
128.4 (2 d, C-1, -2, -4, -5), 131.5 (s, C-11), 133.3 (s,
Flavour Fragr. J. 2001; 16: 50–60

Scheme 2
C-3), 147.9 (s, C-6), 171.0 (s, CO). GC–MS (MAT):
m/z (%) 260 (5, MC ), 200 (19), 190 (26), 177 (29), 158
(14), 148 (34), 144 (27), 143 (30), 131 (31), 129 (18),
118 (79), 117 (37), 115 (23), 105 (21), 95 (8), 91 (31),
83 (31), 79 (13), 77 (13), 69 (32), 67 (13), 55 (100).
Results
Helifolenoic Acids
As already mentioned,1 the lantana oil contains about
0.7% of acidic compounds. However, only traces of
the helifolenoic acids 1a–5a are present in the acidic
part (GC–MS), therefore, 1a–5a were isolated from
an autoxidized fraction of the corresponding helifole-
nals (1–5, R D CHO)1 after repeated FC. The methyl
esters 1b–5b were prepared with diazomethane as usual.
Although even repeated FC did not provide the pure
isomers, structural assignment was undoubtedly pos-
sible by the 1 H- and 13 C-NMR spectra in compari-
son with those of the previously1,2 isolated aldehydes.
Acids 1a–5a might be artefacts, formed during work-
up from the corresponding helifolenals (altogether about
Copyright  2001 John Wiley & Sons, Ltd.
ACIDIC PART OF COMMERCIAL LANTANA OIL 57
Scheme 3
7%), which belong to the main constituents of the lan-
tana oil.
Helifolanols, Helifolanes
LiAlH4 reduction of esters 1b–4b gave the correspond-
ing helifolenols (1–4, R D CH2 OH), already described.1
These four alcohols were hydrogenated on Pd/C to fur-
nish two helifolanols 6 with anti position and 7 with
syn position of the 7-methyl and 11-CH2 OH groups.
Although only mixtures of 1b–4b were used, the results
of the conversion of mixtures with various isomeric
ratios confirmed that 6 was formed from 1b and 3b
and 7 from 2b and 4b. A 2 : 1 mixture of 6/7 was
acylated to the thionocarbonates, radicalic deoxygena-
tion with tris(trimethylsilyl)silane3 then afforded a 2 : 1
mixture of the parent hydrocarbons, the anti- (8) and
syn-helifolane (9, syn. khusiane or ent-allo-cedrane).
Khusiane (7-epi-helifolane, 9) was prepared in 1978
from the secondary alcohol khusiol (ent-allo-cedrol), a
constituent of Indian vetiver oil (khus oil).4 Compar-
ison of the 1 H-NMR spectra of the helifolanols 6/7
with those of the helifolenols (1–4, R D CH2 OH),1
and of the helifolanes 8/9 with those of the heli-
folenes (1–4, R D Me)2 reveals a large effect concerning
the chemical shift of the 3-methyl group. Due to the
anisotropy of the double bond, the 3-methyl group is the
most downfield-shifted methyl group (υ 1.0–1.2) in all
Flavour Fragr. J. 2001; 16: 50–60
58 P. WEYERSTAHL, H. MARSCHALL AND C. CHRISTIANSEN
helifolene derivatives. By contrast, the values of the 3-
methyl group (υ 0.7) of the helifolanes 6–9 are shifted
about 0.4 ppm upfield.
Comparison of the 13 C-NMR data of the anti-helifol-
anes 6 and 8 vs the syn-compounds 7 and 9 displays
the anti 7-methyl group (υ 14.3) shifted about 3 ppm
upfield (see Table 3) compared with the syn 7-methyl
group (υ 17.5), an effect known from the corresponding
helifolene derivatives.1,2
Scheme 4
Copyright  2001 John Wiley & Sons, Ltd.
Methyl Formyl-helifolenoates
The bifunctionalized helifolenes 10, 12, 14, 16 were iso-
lated from a medium polar subfraction of the esterified
acidic fraction. The more polar esters 10/12 could be
separated from the less polar main regioisomers 14/16,
but not from each other.
Nevertheless, the assignment of the regio- and stereo-
isomers is quite obvious. The anisotropic effect of the
Flavour Fragr. J. 2001; 16: 50–60
 ACIDIC PART OF COMMERCIAL LANTANA OIL 59

double bond shifts the signal of 7-H (υ 2.10) of the syn-
isomers 12 and 16 strongly downfield in comparison to
the values (υ 1.78) of the anti -isomers 10 and 14 (see
Table 4). On the other hand, the ester group at C-3 of
10 and 12 shifts the 2-H signal (υ 10: 6.61, 12: 6.51)
more downfield than does the aldehyde group at C-3 of
14 (υ 6.29) and 16 (υ 6.19). Furthermore, the ester group
at C-11 of 14 and 16 leads to a 0.5 ppm downfield shift
of the 10-H signal in comparison with that of 10 and
12. The configurational assignment was supported by
the NOED spectra. The aldehydic proton of 10 and 12
exhibits a strong NOE with 10-H, while 1-H of anti-
10 and anti-14 gave a strong NOE with 7-Me; on the
other hand, 1-H of syn-12 showed a NOE with 7-H.
NaBH4 reduction of the formyl esters 10, 12, 14, 16
afforded the hydroxymethyl esters 11, 13, 15, 17. Their
structures were also ascertained by 1 H- and 13 C-NMR
spectra (see Tables 4 and 5). All the 1 H-NMR effects
mentioned above could be observed, being even stronger
for 2-H: υ 6.54 (11), 6.43 (13) vs. υ 5.88 (15), 5.80 (17).
Methyl 6,10-epoxybisabolen-12-oates 18–25
(A–H)
of 11-Me with 4-Hax , indicating an R-configuration at
C-11. The GC–MS of 18–23 and 25 show the follow-
ing strong fragments: m/z 119 (Me–C6 H4 –CHMežC ),
111 (Me–C6 H7 OHžC ), 110 (Me–C6 H7 Ož ) and 88
(Me–CH2 –CO2 Mež ). Isomer 24 has the same RI as 20
and, because it could be detected only in mixtures with
20 by its NMR values, the MS could not be assigned.
The aldehydes (CHO instead of CO2 Me) correspond-
ing to 18–25 are only trace constituents (0.2–0.4%)
of the lantana oil.1 Those with axial methyl group (cf
22–25) were identified in the neutral part of the oil only
by GC–MS.
Curcumene and Cadinane Derivatives
The structures of two new curcumenoates, 26 and 27,
isolated from the first methyl ester fractions, could easily
be determined by the NMR spectra. LiAlH4 reduction
of ester 27 gave ar-curcumen-15-ol (31), which was
converted to its acetate 32. Up to now, 31 and 32 have
not been found in nature.

The less medium polar subfractions of the esterified

acidic fraction contained eight isomers, A–H, of the
methyl 6,10-epoxybisabolen-12-oates. These isomers are
characterized by three stereogenic centres, such as the
relative position of the double bond, the equatorial or
axial position of the 7-methyl group and the steric situ-
ation of the substituents at C-11 relative to C-10. Com-
plete separation of all isomers was impossible, even after
repeated FC, due to the small amount. Sufficient enrich-
ment for configurational assignment could be achieved
for isomer A (18), B (19), C (20) and D (21). Isomers
E–H (22–25) are present in much lower concentrations,
but the characteristic 1 H-NMR (see Table 6) and even
13
C-NMR data for F (23) and G (24) (see Table 7) could
be observed. By combination of all spectral data, assign-
ment of the eight isomers A–H (18–25) was possible.
The four isomers 18–21 (A–D), possessing an equa-
torial 7-methyl group, show signals at υH of about 0.80
and υC 17.3, contrary to the values for 22–25 (E–H),
with υH about 1.00 and υC 14.0 (see Tables 6 and 7)
for the axial 7-methyl group. The 1 H, 13 C-correlation
for compounds 18–21, 23 and 24 provides the posi-
tion of the double bond, i.e. the value of C-1 is about
υ 36.8 for the bisabolenes 18, 20, 24 and the value
of C-5 is about υ 23.5 for the isomers 19, 21, 23.
The relative stereochemistry of the centres C-10 and
Scheme 5
C-11 can be ascertained by the NOED spectra, since
MMX calculations6 for the rotamers reveal that the
conformation of lowest energy in all cases is charac- In addition to 26 and 27, a third ester, 28, was
terized by an anti-position of 10- and 11-H. Thus, 18 identified, which is a known compound, prepared pre-
and 19 exhibit a NOE of 11-Me with 9-Heq , indicat- viously from the ar-curcumen-12-oic acid, which was
ing an S-configuration at C-11, and 20 displays a NOE found in wild tomato leaves (Lycopersicon hirsutum f.

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 50–60
60 P. WEYERSTAHL, H. MARSCHALL AND C. CHRISTIANSEN
glabratum.).5 The aldehydes
-curcumen-15-al (about References
15%), ar-curcumen-15-al (33, about 5%) and (E)-nuci-
feral (about 4%), corresponding to esters 26–28, are
main constituents of the lantana oil.1
As the most polar compound of the methyl ester frac-
tion, the pyrazoline 30 was eluated, formed by reaction
of the ˛,ˇ-unsaturated acid 29 with two equivalents
of CH2 N2 . 29, named ˛-amorphenic acid, has been
described previously as a constituent of costus root oil.7
The 1 H-NMR values of υ 4.48, 4.65, with a geminal cou-
pling constant, J, of 18 Hz, are typical for the protons
at C-16 in the pyrazoline ring.
Copyright  2001 John Wiley & Sons, Ltd.
1. Weyerstahl P, Marschall H, Eckhardt A, Christiansen C. Flavour
Fragr. J. 1999; 14: 15–28.
2. Weyerstahl P, Marschall H, Wahlburg H-C, Christiansen C, Rus-
taiyan A, Mirdjalili F. Flavour Fragr. J. 1999; 14: 121–130.
3. Schummer DG, Höfle G. Synlett 1990; 705.
4. Ganguly RN, Trivedi GK, Bhattacharyya SC. Indian J. Chem.
1978; 16B: 23–26.
5. Breeden DC, Coates RM. Tetrahedron 1994; 50: 11123–11132;
with correction in Tetrahedron 1995; 51: 1533.
6. PC MODEL, Serena Software, version 4.0, Bloomington, IN
47402, USA, 1993.
7. de Rijke D, Traas PC, ter Heide R, Boelens H, Takken HJ. Phyto-
chemistry 1978; 17: 1664–1666.
Flavour Fragr. J. 2001; 16: 50–60