FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fragr. J. 2001; 16: 19–26

Constituents of the essential oil of Solidago gigantea Ait.

(giant goldenrod)
Danuta Kalemba,1∗ Helga Marschall2 and Pascale Bradesi3
1 Instituteof General Food Chemistry, Technical University of Łódź, Stefanowskiego 4/10, 90924 Łódź, Poland
2 Institut
für Organische Chemie, Technische Universität Berlin, Strasse des 17 Juni 135, D-10623 Berlin, Germany
3 Equipe Chimie et Biomasse, URA CNRS 2053, Université de Corse, Route des Sanguinaires, 20000 Ajaccio, France

Received 11 April 2000

Revised 3 July 2000
Accepted 17 July 2000

ABSTRACT: The hydrodistilled essential oil of aerial parts of S. gigantea was investigated by GC, GC–MS and
NMR spectroscopy. Two samples (1990/91, Warsaw, and 1998, Łódź) yielding 0.55% and 70% of essential oil,
were analysed in 1992 and 1998. Ninety constituents (96% of the total oil) were identified in the first sample
and 85 (98%) in the second. ˛-Pinene (7.0/4.1%), myrcene (2.5/2.6%), p-cymene (2.2/0.6%), ( )-bornyl acetate
(4.4/2.9%), ˛- (6.1/4.0%) and -gurjunene (2.5/2.1%) ( )-germacrene D (21.6/23.5%), ( )-ledol (1.2/2.1%),
eudesma-4(15),7-dien-1ˇ-ol (1.9/2.5%) and ( )-cyclocolorenone (8.1/32.4%) are the main constituents. The
structures of three new sesquiterpenes were established by NMR data: epi-torilenol (5˛H, 6ˇH, 7˛H, 8ˇH,
10˛-6,8-cycloeudesm-4(15)-en-l˛-ol, 0.4/0.1%), 1,10-seco-eudesma-4(15),5(10)-dien-1-al (0.9%/trace) and cis-
eudesm-4(10)-en-1-one (0.2%/trace). Copyright  2001 John Wiley & Sons, Ltd.
KEY WORDS: Solidago gigantea Ait.; Asteraceae; essential oil; terpenoids; germacrene D; 6,8-cycloeudesm-
4(15)-en-1-ol; 1, 10-seco-eudesma-4(15),5(10)-dien-1-al; cis-eudesm-4(10)-en-1-one; cyclocolorenone

Introduction flavonoids, phenolic acids and diterpenes, have been

studied by a number of researchers.5,6
As a part of our investigation on essential oils from
four Solidago species growing in Poland, we have
recently reported on the essential oils of S. canadensis,1
Experimental
S. graminifolia2 and S. virgaurea.3 In the present work
Plant Material and Oil Preparation
the essential oil from S. gigantea Ait. has been investi-
gated. S. gigantea Ait. (syn. S. serotina Ait.), giant gold-
The aerial parts of S. gigantea growing wild were
enrod (Asteraceae), is a strong expansive plant of North
collected at the flowering stage in August 1990 and
American origin which is widely distributed in most
1991 in Warsaw (first sample) and 1998 in Łódź (sec-
European countries.4 The medicinal material known
ond sample), in central Poland. Voucher specimens
as Herba Solidaginis includes S. virgaurea, S. gigantea
Nos. SGG90, SGG91 and SGG98 are deposited at
and S. canadensis.5,6 This material and its extracts are
the Institute of General Food Chemistry, Technical
components of many preparations applicable in dis-
University of Łódź. The material was dried at room
eases of the urinary tract, nephrolithiasia and prostate
temperature and hydrodistilled in a glass apparatus
conditions.6 S. gigantea herb extract shows a pronou- for 5 h.
nced anti-inflammatory effect and moderate diuretic and
spasmolytic properties.7
There is only one publication about the constituents of GC, GC–MS and NMR Analysis (Table 1)
the essential oil of S. gigantea, given by Fujita, report-
ing on the presence of germacrene D (66–77%) and GC
bornyl acetate (5–7%) as the main constituents.8 Other
constituents of S. gigantea, namely triterpene saponins, Carlo Erba HRGC 5300 MEGA with a Rtx-1 capillary
column, 30 m ð 0.25 mm i.d., film thickness 0.25 µm;
temperature programme, 60 ° C to 300 ° C at 4 ° C/ min;
*Correspondence to: D. Kalemba, Institute of General Food Chem-
istry, Technical University of Łódź, Stefanowskiego 4/10, 90924 Łódź, injection temperature, 310 ° C; detector (FID) tempera-
Poland. E-mail: [email protected] ture, 300 ° C; carrier gas, N2 , 1 ml/min.

Copyright  2001 John Wiley & Sons, Ltd.

20 D. KALEMBA, H. MARSCHALL AND P. BRADESI

Table 1. Constituents of the essential oil of Solidago gigantea Ait.

Peak no. Compound 1991 (%) 1998 (%) RI Identificationb Reference
1 (E)-2-Hexenal 0.2 t 831 MS
2 (Z)-Hex-1-en-3-ol t t 845 MS
3 Non-1-ene 1.1 0.8 886 MS, 1H
4 ˛-Thujene 0.1 t 928 MS
5 a-Pinene 7.0 4.1 934 MS, 1H

6 Camphene 0.9 0.5 945 MS, 1H

7 Sabinene 1.0 0.3 968 MS, 1H

8 ˇ-Pinene 1.5 0.9 973 MS, 1H

9 Myrcene 2.5 2.6 984 MS, 1H

10 ˛-Phellandrene 0.8 1.5 998 MS, 1H

11 p-Cymene 2.2 0.6 1014 MS, 1H

12 ˇ-Phellandrenea — 0.1 1025 MS, 1H

13 Limonenea 1.0 0.1 1025 MS, 1H

14 -Terpinene t t 1055 MS
15 1-Isopropenyl-4-methylbenzene t t 1078 MS
16 Terpinolene t t 1083 MS
17 cis-Sabinene hydrate 0.2 t 1087 MS, 1H
18 Linalol 0.1 t 1089 MS
19 ˛-Campholene aldehyde 0.2 0.1 1108 MS, 1H

20 cis-Verbenol 0.2 t 1130 MS, 1H

21 trans-Pinocarveol — t 1130 MS, 1H

22 ( )-trans-Verbenolc 0.4 0.1 1135 MS, 1H

23 Borneol 0.1 t 1156 MS
24 Terpinen-4-ol 0.3 0.2 1168 MS, 1H

25 Myrtenal 0.1 t 1175 MS, 1H

26 ˛-Terpineol 0.1 0.1 1179 MS, 1H

27 Myrtenol 0.1 t 1184 MS, 1H

28 Verbenone 0.2 0.1 1186 MS, 1H

29 trans-Carveol t t 1204 MS
30 Carvone 0.1 t 1219 MS, 1H

31 (−)-Bornyl acetated 4.4 2.9 1273 MS, 1H

32 p-Cymen-7-ola 0.3 0.2 1273 MS, 1H

33 Thymola 0.2 0.2 1273 MS
34 Carvacrol 0.2 0.1 1283 MS, 1H

35 υ-Elemene 0.3 0.4 1337 MS, 1H

36 Eugenol t — 1337 MS
37 ˛-Cubebene 0.2 t 1355 MS, 1H

38 Cyclosativene 0.1 t 1373 MS, 1H

39 ˛-Ylangene t t 1373 MS, 1H

40 (Z)-Jasmone t — 1373 MS, 1H

41 ˛-Copaene 0.2 0.2 1379 MS, 1H

42 ˇ-Cubebene — 0.2 1387 MS, 1H

43 ˇ-Bourbonenea 0.6 t 1387 MS, 1 H, 13 C

44 ˇ-Elemenea 1.3 1.7 1387 MS, 1 H, 13 C

45 a-Gurjunene 6.1 4.0 1411 MS, 1 H, .13 C/

46 ˇ-Caryophyllene 1.3 1.2 1417 MS, 1H

47 -Elemene 0.4 0.4 1427 MS
48 Aromadendrene 0.4 0.3 1441 MS
49 ˛-Humulene 0.5 0.5 1451 MS, 1 H, (13 C)

50 g-Gurjunenea 2.5 2.1 1471 MS, 1 H, (13 C)

51 -Muurolenea 1.6 1.0 1471 MS, 1 H, (13 C)

52 (−)-Germacrene De 21.6 23.5 1482 MS, 1 H, .13 C/

53 ˇ-Selinene 0.4 t 1485 MS, (13 C)

54 4-epi-Cubebol 0.6 — 1489 MS, 1H
55 Ledene — t 1493 MS
56 Bicyclogermacrene 1.7 1.7 1494 MS, 1 H, (13 C/

57 ˛-Muurolene 0.2 0.2 1499 MS, (13 C)

58 -Cadinene 0.9 0.3 1508 MS, (13 C)
59 d-Cadinene 1.9 0.8 1516 MS, (13 C)
60 ˛-Calacorenea 0.1 0.1 1533 MS
61 cis-Dracunculifoliola 0.2 — 1533 MS 18
62 exo-1,5-Epoxysalvial-4(14)-ene (mint oxide) 0.1 t 1540 MS 19
63 epi-Torilenol 0.4 0.1 1546 MS, 1H

64 endo-1,5-Epoxysalvial-4(14)-ene 0.2 0.1 1551 MS, 1 H, (13 C) 19, 20

(sage oxide)a

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
 ESSENTIAL OIL OF SOLIDAGO GIGANTEA 21

Table 1. Continued
Peak no. Compound 1991 (%) 1998 (%) RI Identificationb Reference
65 (E)-Nerolidola 0.3 0.1 1551 MS, 1 H, (13 C)
66 Germacrene B 0.1 t 1555 MS
67 ( )-Palustrol 0.6 0.6 1565 MS, 1 H, (13 C) 13
68 Spathulenol 1.9 1.0 1569 MS, 1 H, (13 C)

69 Caryophyllene epoxidea 0.5 0.2 1574 MS, 1 H, (13 C)

70 1, 10-seco-Eudesma-4(15),5(10)-dien-1-ala 0.9 t 1574 MS, 1 H, 13 C

71 cis-Eudesm-4(15)-en-1-one 0.2 t 1574 MS, 1 H,13 C

72 Globulol 0.4 — 1582 MS
73 Salvial-4(14)-en-1-one 0.2 t 1584 MS, 1H 20, 21
74 Viridiflorol 0.4 0.4 1586 MS, 1 H, (13 C/
75 trans-Dracunculifoliol 0.1 — 1586 MS 18
76 Humulene epoxide II 0.1 t 1597 MS, 1 H, (13 C/

77 Torilenola 0.5 0.5 1599 MS, 1H 15, 22

78 (−)-Ledola,g 1.2 2.1 1599 MS, 1 H, (13 C)
79 ˛-Corocalene 0.4 0.1 1602 MS
80 Salvia-4(14),5-dien-1ˇ-ol 0.5 0.4 1605 MS, 1H 21
81 Guaia-6,10(14)-dien-4ˇ-ol 1.4 0.3 1614 MS, 1H 23
82 10-epi-Cubenol 0.3 0.1 1626 MS, (13 C)
83 T-Cadinol 0.3 0.3 1631 MS, 1 H, (13 C)

84 T-Muurolola 0.1 0.9 1633 MS, 1 H, (13 C)

85 (C)-Opposita-4(15),7(11)-dien-1ˇ-ola 0.7 — 1633 MS, 1 H, 13 C 15, 24

86 Opposita-4(15),11-dien-1ˇ-ol 1.4 — 1642 MS, 1 H, 13 C 15, 24
87 ˛-Cadinol 1.0 1.3 1644 MS, 1 H, (13 C/
88 ˇ-Eudesmol 0.9 — 1648 MS
89 Cadalene 0.2 t 1660 MS
90 Guaiazulene 1.2 t 1664 MS
91 Eudesma-4(15),7-dien-1b-ol 1.9 2.5 1673 MS, 1H 25
92 ˇ-Dictyopterol 0.2 — 1706 MS, 1H 26, 27
93 Mintsulphide 0.2 0.1 1730 MS, 1 H, 13 C 28
94 (−)-Cyclocolorenonei 8.1 32.4 1740 MS, 1 H, 13 C 17, 29, 30
95 Hexahydrofarnesylacetone — 0.1 1823 MS
t D trace (<0.1%).
a percentage determined on DB-Wax column.
b 13
C D identification of isolated component, (13 C/ D identification from a mixture in FC fractions.
c [˛]22
D 68 ° (c D 2.0, CHCl3 , GC: 72%), reference 11: 134.5 °
d
[˛]22
D 35.5 ° (c D 3.8, CHCl3 , GC: 92%), reference 12: 39°
e
[˛]22
D 260 ° (c D 1.5, CHCl3 , GC: 92%), reference 10: [˛]D 20 240 °
f
[˛]22
D 21.7 ° (c D 2.4, CHCl3 , GC: 83%), reference 13: 17.8 °
g
[˛]22
D 9.6 ° (c D 1.3, CHCl3 , GC: 88%), reference 14: 10.5 °
h [˛]22 C 15.5 ° (c D 4.0, CHCl , GC: 90%), reference 15: C29.3 °
D 3
i
[˛]22
D 425° (c D 7.7, CHCl3 , GC: 96%), reference 16: 400° , reference 17: 446°

GC–MS Isolation, Separation and Identification of

Compounds
Fisons MD 800 combined with GC 8000, ionization volt-
age 70 eV; ion source temperature, 220 ° C; carrier gas, The essential oils from 1990 and 1991 (55 g, separated
He, 40 ml/min; GC conditions were the same as for the and analysed in Berlin, 1991/92) and from 1998 (28 g,
analytical GC. Retention indices (RI) were calculated by separated and analysed in Łódź, 1998/99) were distilled
comparing the retention times of the eluting peaks with with a 30 cm and 20 cm Vigreux column, respectively.
those of C7 –C19 alkanes. The first sample gave the following fractions: (a) b.p.
45–52 ° C/ 22 Torr, 3.6 g, monoterpene hydrocarbons;
1
(b) b.p. 40–50 ° C/ 0.8 Torr, 5.0 g, oxygenated monoter-
H-NMR (CDCl3 ) penes; (c) b.p. 50–65 ° C/ 0.1 Torr, 10.5 g, germacrene D
(52, 45%), ˛-gurjunene (45, 20%); (d) a residue, 32 g.
Bruker DPX 250 and Bruker AM 400; 13 C-NMR The second sample gave the following fractions:
.CDCl3 /: Bruker DPX 250 and Bruker AH 270, both (a) b.p. 22–35 ° C/ 15 Torr, 2.0 g, monoterpene hydro-
with DEPT programme; 13 C-NMR of sesquiterpene FC carbons; (b) b.p. 60–80 ° C/ 0.8 Torr, 0.5 g, oxygenated
fractions (second sample): Bruker AC 200, computer- monoterpenes; (c) b.p. 80–95 ° C/ 0.8 Torr, 10.5 g, ger-
aided analysis by comparing the signals obtained with macrene D (52, 51%), ˛-gurjunene (45, 14%); (d) a
those of pure compounds.9 residue 14.2 g, cyclocolorenone (94, 60%).

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
22 D. KALEMBA, H. MARSCHALL AND P. BRADESI

The distillation fractions obtained in 1992 and 1998, Opposita-4(15),7(11)-dien-1ˇ-ol (85)

respectively, were each further separated by repeated
flash chromatography (FC) on ICN Silica 32–63 and GC: 90%. 1 H-NMR .CDCl3 [C6 D6 ]/: υ 0.68 [0.81] (s,
ICN Silica impregnated with silver nitrate with pentane 10-Me), 1.33 [1.44] (dddd, J D 13, 11, 7, 2 Hz, 8-H),
(monoterpenes) or hexane (sesquiterpenes) and increas- 1.43 [1.36] (ddd, J D 11, 11, 7 Hz, 9-H), 1.51 [1.47]
ing amounts of diethyl ether up to 80%, with monitor- (dddd, J D 13, 11, 11, 5 Hz, 2-Hax ), 1.66 [1.60] (d, br.,
ing by TLC and GC. The fractions were subjected to J D 11 Hz, 5-Hax ), 1.67 (d, J D 1 Hz, 11-Me2 ), [1.66,
GC–MS, 1 H- and 13 C-NMR analysis and the fractions 1.70, 2 d, J D 1 Hz, 11-Me2 ], 1.71 [1.70] (ddd, J D 11,
from sample 2 to computer-aided 13 C-NMR analysis (in 9, 2 Hz, 90 -H), 1.80 [1.60] (dddd, J D 13, 5, 5, 2 Hz, 2-
Ajaccio) additionally. Heq ), 2.05 [1.93] (ddd, br., J D 14, 13, 5 Hz, 3-Hax ),
2.05 [2.06] (dddd, J D 13, 11, 9, 7 Hz, 80 -H), 2.28
Epi-Torilenol (5˛H,6ˇH,7˛H,8ˇH, [2.18] (ddd, J D 14, 5, 2 Hz, 3-Heq ), 2.84 [2.95] (dddd,
10˛-6,8-cycloeudesm-4(15)-en-1˛-ol, 63) J D 11, 11, 9, 7 Hz, 6-H), 3.57 [3.29] (dd, J D 11, 5 Hz,
1-Hax ), 4.47, 4.79 [4.73, 4.92] (2 ddd, J D 1.5, 1.5,
GC: 60%, mixture with ledol (78) and salviadienol (80). 1.5 Hz, 4-CH2 ), 4.97 [5.11] (dqq, J D 9, 1, 1 Hz, 7-
1
H- and 13 C-NMR: Table 2. GC–MS: m/z (%) 220 H); reference 24: υ.CDCl3 / 0.68, 1.66, 3.55, 4.47, 4.79,
(5, MC ), 205 (4), 202 (4), 187 (5), 177 (7), 163 (18), 4.97. 13 C-NMR: The data are identical with those given
159 (26), 146 (28), 145 (25), 131 (58), 124 (54), 123 in reference 15. GC–MS: m/z (%) 220 (4, MC ), 205 (6),
(100), 120 (34), 119 (34), 109 (60), 107 (34), 105 (68), 202 (3), 187 (5), 177 (24), 159 (10), 146 (17), 133 (24),
96 (32), 93 (54), 91 (70), 81 (64), 79 (46), 77 (37), 67 132 (21), 123 (72), 120 (38), 107 (30), 106 (33), 105
(35), 55 (52). (31), 96 (48), 95 (50), 91 (46), 82 (100), 81 (65), 79
(47), 77 (33), 67 (72), 55 (46).
Torilenol (5˛H,6ˇH,7˛H,8ˇH,10ˇ-6,8-cycloeudesm-
4(15)-en-1ˇ-ol, 77) Opposita-4(15),11-dien-1ˇ-ol (86)

GC: 75%, mixture with ˛-cadinol (87, 15%). 1 H- and GC: 50%, mixture with torilenol (70, 30%) and ˛-
13
C-NMR: Table 2. GC–MS: m/z (%) 220 (5, MC ), 205 cadinol (87, 15%). 1 H-NMR .CDCl3 [C6 D6 ]/: υ 0.66
(7), 202 (6), 187 (11), 177 (13), 163 (18), 159 (58), 146 [0.75] (s, 10-Me), 1.37 [1.37] (mc , 8-, 9-H), 1.51 (dddd,
(33), 145 (52), 133 (34), 131 (94), 121 (34), 120 (42), J D 13, 11, 11, 5 Hz, 2-Hax ), 1.70 [1.68] (d, br., J D
119 (49), 117 (44), 107 (50), 106 (38), 105 (90), 93 (76), 14 Hz, 90 -H), 1.71 [1.68] (d, br., J D 13 Hz, 7-H), 1.74
92 (56), 91 (100), 81 (50), 80 (42), 79 (72), 77 (62), 67 [1.72] (s, br., 11-Me), 1.80 (dddd, J D 13, 5, 5, 2 Hz,
(58), 55 (70), 53 (39). 2-Heq ), 2.05 [1.92] (ddd, br., J D 14, 13, 5 Hz, 3-Hax ),

Table 2. 1 H- and 13 C-NMR values of epi-torilenol (63) and torilenol (6,8-cycloeudesm-4(15)-en-1 ˇ-ol, 77) (for
numbering, see Scheme 1)

υC .C6 D6 / υH 63 υH 77
a b
C/H no. 63 77 C6 D6 CDCl3 J [Hz] C6 D6 CDCl3 c J [Hz]
1ax d 72.0 77.0 3.72 3.87 dd 12;4 3.26 3.52 dd 11;5
2ax t 32.1 31.6 1.43 1.43 dddd 13; 13; 12; 5 1.42 1.45 dddd 13; 13; 11; 5
2eq 1.63 dbr. 13 1.54 1.75 dddd 13; 6; 5; 2
3ax t 31.0 34.3 2.15 dddd 13; 13; 5; 1.5 1.86 2.00 ddddd 14; 13; 6; 1.5
3eq 2.22 2.32 ddbr. 13; 5 2.16 2.28 ddd 14; 5; 2
4 s 147.1 146.4
5 d 60.8 58.0 1.97 1.92 dbr. 3.5 1.43 1.48 dbr. 5
6 d 31.6 24.8 1.05 ddd 7; 3.5; 3 1.28 1.26 ddd 7; 5; 3
7 d 47.6 48.7 0.47 0.48 ddd 9; 3; 3 0.50 0.52 ddd 9; 3; 3
8 d 24.7 24.9 1.10 dddd 7;,7; 5; 3 1.10 1.18 dddd 7; 7; 6; 3
9 t 41.8 43.1 0.95 dd 13; 5 0.99 1.02 dd 12; 6
90 2.39 2.23 dd 13; 7 2.02 1.96 dd 12; 7
10 s 58.5 59.6
11 d 32.3 32.7 0.82 dqq 9; 6.5; 6.5 0.84 0.90 dqq 9; 6.5; 6.5
4-CH2 t 110.2 105.7 4.81 4.68 dd 1.5; 1 4.90 4.80 ddd 1.5; 1.5; 1.5
dbr. 4.72 dd 2; 2 4.93 4.82 ddd 1.5; 1.5; 1.5
10-Me q 16.2 14.1 0.89 0.76 s 0.98 0.80
11-Me q 21.6 22.0 0.99 0.91 d 6.5 1.015 d 0.93 o 6.5
s
11-Me q 21.7 22.1 1.00 0.92 d 6.5 1.01 d 0.93 6.5
a
With 1 H13 C correlation.
b In agreement with the values .CDCl3 / given in reference 22.
c
Reference 22: υ.CDCl3 / 0.52 (s br.), 0.80 (s, Me), 0.94 (s, 2 Me), 3.48 (dd, J D 11, 5 Hz), 4.78 (s br.).

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
 ESSENTIAL OIL OF SOLIDAGO GIGANTEA 23

Table 3. 1 H-NMR values of 1,10-seco-eudesma-4(15),5(10)-dien-1-al (70) and its derivatives B and C

(for numbering, see Scheme 3)

70 B C
H no. CDCl3 C6 D6 CDCl3 C6 D6 CDCl3 C 6 D6 J [Hz]
1 9.76a 9.38a 3.66b 3.42b 4.07b,c 4.07b,d
2 2.47 2.05 1.65 1.60 1.70 1.75 td 7; 1
3 2.47 2.32 2.18 2.24 2.16 2.18 tbr. 7
6, 60 2.00, 1.98 2.05 2.00 2.02 2.02 2.00 mc
7 1.28 1.35 1.30 1.35 1.28 1.35 mc
8 1.75 1.68 1.73 1.72 1.74 1.70 dbr. 12
80 1.17 1.18 1.18 1.24 1.19 1.21 dddd 12; 11; 8; 6
9 2.00 1.96 2.00 2.18 2.00 2.13 ddbr. 15; 12
90 1.75 1.82 1.98 1.93 1.98 1.88 dbr. 15
11 1.45 1.42 1.45 1.42 1.46 1.45 qqd 7; 7; 7
4-CH2 4.69 4.78 4.65 4.88 4.67 4.85 dt 1.5; 1
4.92 4.88 4.92 5.06 4.91 5.01 dt 1.5; 1
10-Me 1.59 1.65 1.61 1.76 1.61 1.72 sbr.
11-Me 0.88 0.91 0.89 0.92 0.88 0.92 d 7
11 Me 0.89 0.91 0.895 0.92 0.89 0.92 d 7
a
t, J D 1 Hz.
b t, J D 7 Hz.
c
OAc: υ 2.05, s.
d
OAc: υ 1.72, s.

2.20 [2.25] (ddddd, J D 13, 10, 10, 5, 3 Hz, 6-H), 2.28 220 (16, MC ), 202 (12), 187 (8), 177 (25), 164 (24), 159
[2.17] (ddd, J D 14, 5, 2 Hz, 3-Heq ), 2.38 [2.50] (d, br., (63), 135 (37), 134 (40), 133 (31), 132 (32), 131 (28),
J D 13 Hz, 70 -H), 3.55 [3.28] (dd, J D 11, 5 Hz, 1-Hax ), 121 (41), 120 (43), 119 (35), 118 (35), 117 (36), 107
4.57, 4.85 [4.69, 4.89] (2 ddd, J D 15, 1.5, 1.5 Hz, 4- (61), 106 (63), 105 (57), 95 (35), 94 (28), 93 (94), 91
CH2 ), 4.69, 4.71 [4.86, 4.87] (2 s, br., 11-CH2 ); reference (100), 81 (50), 79 (56), 77 (48), 69 (28), 67 (47), 55
24: υ.CDCl3 / 0.66, 1.76, 3.58, 4.61, 4.73 (2 H), 4.89. (70), 53 (32).
13
C-NMR: The data are identical with those given in
reference 15. GC–MS: m/z (%) 220 (2, MC ), 205 (6), 1,10-Seco-Eudesma-4(15),5(10)-dien-ol (B)
202 (7), 187 (10), 176 (43), 161 (34), 147 (46), 146
(60), 131 (55), 121 (50), 120 (43), 119 (48), 107 (60),
Prepared from 70 with NaBH4 as usual. 1 H- and 13 C-
106 (51), 105 (100), 93 (78), 92 (52), 91 (92), 81 (74),
NMR: Tables 3 and 4. GC–MS: m/z (%) 222 (18,
80 (52), 79 (90), 77 (60), 67 (60), 55 (95), 53 (52).
MC ), 207 (20), 178 (25), 135 (60), 121 (31), 120
Salvia-4(14),5-dien-1-ol (80) (31), 119 (42), 107 (71), 106 (69), 105 (68), 95 (40),
1
H-NMR .CDCl3 [C6 D6 ]/ : υ 0.88, 0.90 [0.90, 0.92] (2 d,
Table 4. 13 C-NMR values of 1,10-seco-eudesma-
J D 7 Hz, 11-Me2 ), 0.90 [1.07] (s, 10-Me), 2.35 [2.25] 4(15),5(10)-dien-1-al (70) and its derivatives B and C
(ddd, J D 14, 5, 2 Hz, 3-H), 3.46 [3.30] (dd, J D 11, and of cis-eudesm-4(15)-en-1-one (71) (for numbering,
4 Hz, 1-H), 4.63 [4.72] (dd, J D 2.5, 2.5 Hz) and 4.81 see Scheme 3)
[5.00] (dd, J D 2.5, 2.5 Hz, 4-CH2 ), 5.57 [5.73] (dd,
70a Ba Cb 71
J D 2, 1.5 Hz, 5-H), in agreement with the data .CDCl3 / C no. C6 D6 CDCl3 C6 D6 CDCl3
given in reference 21. 13 C-NMR: υ 17.3 (q, 10-Me), 19.0,
1 d 200.1 t 62.9 t 64.1 s 214.7
19.5 (2 q, 11-Me2 ), 20.9, 30.2, 32.3, 35.1 (4t), 42.2 (d, C- 2 t 41.8 30.9 27.2 t 37.9
7), 61.0 (s, C-10), 78.9 (d, C-1), 109.5 (t, C-14), 126.5 (d, 3 t 28.3 31.9 32.2 t 34.3
C-5), 147.9 (s, C-4 or C-6), 1 ð s, C-6 or C-4, intensity 4 s 150.0 151.0 150.6 s 147.4
5 s 128.2 124.4 128.3 d 54.5
too low; GC–MS: m/z (%) 220 (6, MC ), 205 (6), 202 6 t 32.2 32.1 32.2 t 30.0
(6), 187 (7), 177 (8), 163 (15), 159 (20), 146 (42), 131 7 d 40.9 40.7 41.0 d 43.9
(50), 124 (30), 123 (86), 119 (43), 109 (71), 107 (50), 8 t 26.6 26.4 26.7 t 26.4
9 t 33.7 33.4 33.7 t 34.4
105 (82), 93 (68), 91 (100), 81 (68), 79 (75), 67 (50), 10 s 132.6 132.7 133.0 s 49.3
55 (78), 53 (44). 11 d 32.4 32.2 32.4 d 32.7
4-CH2 t 112.2 111.4 112.1 t 111.2
1,10-Seco-Eudesma-4(15),5(10)-dien-1-al (70, 10-Me q 20.3 20.2 20.2 q 27.7
Scheme 3) 11-Me q 19.9 19.85 19.8 q 19.8
11-Me q 19.9 19.8 19.9 q 19.8
IR:  3075, 1635 .D CH2 /, 2715, 1730, (CHO) cm 1 . a
With 1 H13 C correlation.
1
H- and 13 C-NMR: Tables 3 and 4. GC–MS: m/z (%) b
OAc: 170.1 (s), 20.5 (q).

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
24 D. KALEMBA, H. MARSCHALL AND P. BRADESI

94 (38), 93 (100), 92 (27), 91 (72), 81 (49), 80 Eudesm-4(15)-en-1-one (71)

(48), 79 (51), 77 (42), 69 (57), 67 (43), 55 (65),
1
53 (26). H-NMR (from the 2:1 mixture with 70; CDCl3 ): υ 0.82,
0.83 (2 d, J D 7 Hz, 11-Me2 ), 1.11 (s, 10-Me), 1.05,
1,10-Seco-Eudesma-4(15),5(10)-dien-1-ol 1.35, 1.55, 1.65, 1.70 (5 mc , 7-H), 2.28, 2.32 (2 mc ,
acetate (C) 4 H), 2.59 (ddd, J D 14, 13, 7 Hz, 2-Hax ), 2.68 (ddddd,
J D 13, 13, 6, 2, 2 Hz, 3-Hax ), 4.88 (d, J D 2 Hz, 4-
Prepared from alcohol B with Ac2 O and DMAP as usual. CH2 ). 1 H-NMR .C6 D6 / : υ 0.84, 0.85 (2 d, J D 7 Hz,
1
H- and 13 C-NMR: Tables 3 and 4. GC–MS: m/z (%) 11-Me2 ), 0.99 (s, 10-Me), 1.32, 1.45, 1.55, 2.09 (4 mc ,
264 (14, MC ), 204 (4), 189 (18), 161 (38), 133 (30), 120 8 H), 2.09 (dd, br., J D 13, 4 Hz, 5-Hax ), 2.19 (ddd,
(30), 119 (52), 107 (37), 106 (37), 105 (100), 93 (52), J D 14, 7, 2 Hz, 3-Heq ), 2.31 (ddd, J D 14, 13, 7 Hz,
92 (52), 91 (58), 81 (28), 79 (35), 77 (28), 69 (38), 67 2-Hax ), 2.43 (dddd, J D 13, 13, 6, 2, 2 Hz, 3-Hax ), 2.60
(28), 55 (45). (ddd, J D 14, 3, 3 Hz, 2-Heq ), 4.76 (dd, J D 2, 2 Hz)

Scheme 1. Only relative configurations are shown

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
 ESSENTIAL OIL OF SOLIDAGO GIGANTEA 25

and 4.79 (dd, J D 2, 1 Hz, 4-CH2 ). 13 C-NMR: Table 3.

GC–MS: m/z (%) 220 (2, MC ), 205 (1), 177 (3), 136
(40), 124 (18), 123 (100), 122 (16), 107 (16), 105 (15),
95 (18), 93 (25), 91 (24), 81 (24), 79 (26), 69 (17), 67
(20), 55 (28), 53 (16).

Results and Discussion

A dark yellow essential oil was obtained from two
samples of aerial parts (flowers, leaves and stems) of
S. gigantea harvested in Warsaw (1990/91) and Łódź
(1998) with a yield of 0.55% and 0.70%, respectively.
The odour of the oil was fresh, herbaceous, aggres-
sive, suffocating conifer-like, slightly fruity, cedar-like,
woody-minty.
Ninety constituents (96% of the total oil) were iden-
tified in the first, and 85 (98%) in the second sam-
ple (Table 1). ˛-Pinene (5), myrcene (9), p-cymene
(11), ( )-bornyl acetate (31), ˛- (45) and -gurjunene
(50), ( )-germacrene D (52), ( )-ledol (78), eudesma-
4(15),7-dien-1ˇ-ol (91) and ( )-cyclocolorenone (94)
are the main constituents. Previously, it has been demon- Scheme 2. Possible pathway to cis-(63) and trans-cyclo-
strated that the oils of S. gigantea,8 and of other Solidago eudesmenol (77)
species1 – 3,10 are a rich source of germacrene D (52).
The essential oils of S. altissima,10 S. canadensis and
structure of 70 follows from the 1 H- and 13 C-NMR
S. gigantea31,32 of different origin consisted of (C)- and
data (Tables 3 and 4) including 1 H13 C correlation. We
( )-germacrene D in different ratios, while this oil con-
propose that seco-eudesmadienal 70 might be biogeneti-
tained obviously only ( )-germacrene D (52).
cally formed by fragmentation of cis-diol D (Scheme 3).
The oil of S. gigantea contains many compounds
NaBH4 reduction of 70 yielded alcohol B which reacted
(73, 77, 80, 85, 86) which were previously obtained
with acetic anhydride/dimethylaminopyridin (DMAP) to
by biomimetic reactions of germacrene D epoxide
give acetate C.
A21,24 and also isolated from Torilis japonica D. C.
Ketone 71 revealed 1 H-NMR values (υ 0.82, 0.83, 2
(Japanese name Tabujirami).15,22 Even the mint oxides
d, J D 7 Hz, 2 Me, 1.11, s Me, 4.76, 4.79, H2 C D C)
(62, 64),19,20 mint sulphide (93),28 the dracunculifoliols
which were not identical with those given for compound
61, 7518 and the eudesmadienols 91, 9225,27 might be
E (υ 0.89, 0.90, 2 d, 2 Me, 0.96, s, Me, 4.76, 4.98,
subsequent products of germacrene D (52).
H2 C D C).33,34 Therefore, only a cis-eudesmenone struc-
In addition to the known 6,8-cycloeudesmenol (‘tori-
ture is possible. Typically of the cis ring junction is the
lenol’) 77, we identified a compound 63, which showed 13
1 C-NMR value of the 10-methyl group (υ 27.7), with
H- and 13 C-NMR data very similar to alcohol 77
the corresponding υ-value of trans-octalones should be
(Table 2). Therefore, the structure of an epi-torilenol
around 20 ppm.35 Epoxide A0 might also be the precur-
(63) was formulated. The configuration was established
sor of ketone 71.
by the NOED spectra. Contrary to 77 we observed a
( )-Cyclocolorenone (94) was isolated previously
strong NOE between 5-H (υ 1.97) and the 10-Me group
from Pseudowintera colorata,16 Ledum palustre36 and
.υ 0.89/, while another strong NOE existed between 5-H
from Solidago canadensis,37 while ent-94 was identified
and 7-H .υ 0.47/, which was also apparent in torilenol
in liverworts.29 Jacyno et al. 30 reported on the phy-
(77, Scheme 2). Therefore, alcohol 63 is a 1,5,10-epi-
totoxic and antimicrobial properties of 94, which was
torilenol with a 5,10-cis-6,8-cycloeudesmane skeleton.
extracted from the leaves of the Magnolia grandiflora
A pathway from germacrene epoxide A to torilenol
L. tree.
was formulated by Niwa et al.22 We propose that the
diastereomeric epoxide A’ might be the precursor of epi-
torilenol (63). References
Furthermore, we isolated two other new sesquiter-
penes, an aldehyde 70 (υH 9.76, υC 200.1, d) and a 1. Weyerstahl P, Marschall H, Christiansen C, Kalemba D, Góra J.
Planta Med. 1993; 59: 281.
ketone 71 (υC 214.7). The latter could not be separated 2. Kalemba D, Weyerstahl P, Marschall H. Flavour Fragr. J. 1994;
completely from aldehyde 70. The seco-eudesmadiene 9: 269.

Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26
26 D. KALEMBA, H. MARSCHALL AND P. BRADESI

Scheme 3. Only relative configurations are shown

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Copyright  2001 John Wiley & Sons, Ltd. Flavour Fragr. J. 2001; 16: 19–26