FLAVOUR AND FRAGRANCE JOURNAL

Flavour Fra`r[ J[ 1999^ 04] 042Ð062

Analysis of the polar fraction of Haitian vetiver oil

Peter Weyerstahl, Helga Marschall, Ute Splittgerber and Dietmar Wolf
Institut für Organische Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany

Received 10 September 0888

Accepted 5 January 1999

ABSTRACT] The polar part of commercial Haitian vetiver oil was converted to the methyl ethers\ and this
product separated by distillation and repeated ~ash chromatography "FC#[ The following new "nor!# ses!
quiterpene alcohols were isolated as their methyl ethers and identi_ed by their 0H! and 02C!NMR spectra] 01!
nor!ziza!5"02#!en!1b! "1# and !1a!ol "2#\ eudesma!3"04#\6!dien!2b! "6# and !1b!ol "07#\ eudesma!2\4!dien!0a!ol
"15#\ eremophila!0"09#\3"04#!dien!1a!ol "20#\ eremophila!0"09#\00!dien!1a!ol "nootkatol\ 27#\ guaia!0"4#\00!dien!
2!ol "00#\ spirovetiva!2\6"00#!dien!01!ol "31#\ preziza!6"04#!en!2a!ol "03# and helifol!0!en!03!ol "syn[ khusien!03!
ol\ 01#[ Furthermore\ the hemi!acetal 6\09!epoxy!salvialan!09!ol "7# was identi_ed[ The structure of some artefacts
formed by alkylation of b!vetivone 41 ":M 28\ M 32# and of 00\01\02!tri!nor!eudesmenone ":05\ 06# was also
elucidated[ Copyright Þ 1999 John Wiley + Sons\ Ltd[

KEY WORDS] vetiver oil^ essential oil^ Vetiveria zizanioides "L[# Nash^ sesquiterpene alcohols^ methyl ether
derivatives^ NMR

Introduction
Recently\ we reported on the investigation of the med!
ium polar part of commercial Haitian vetiver oil\ par!
ticularly with regard to carbonyl compounds[0 We
mentioned that we converted the main alcohols of a
medium polar to polar fraction to the corresponding
methyl ethers[ Thus\ the existence of new alcohols i[e[
b!funebren!03!ol "02# and prezizaen!01!ol "18#\ besides
the known alcohols cyclocopacamphanol "3\ 5#\
khusimol "29# and isovalencenol "30#\ was established
"Scheme 0#[ The occurrence of two other methyl ethers
M 8\ M 21 ðviz[ alcohols 3\6!epoxy!spirovetiv!1!en!00!
ol "8# and cis!eudesma!5\00!dien!2b!ol "21#Ł and of the
amorph!3!en!09!ols was described earlier[1Ð3 Now\ we
wish to communicate the analysis of this transformed
fraction and the identi_cation of its constituents[

Experimental
0
H!NMR "CDCl2#] Bruker AM 399[ 02C!NMR] Bruker
AH 169 with DEPT program[ GCÐMS] Hewlett Pack!
ard HP 4789 II "01[4 m HP!0 column# combined with
HP 4860 A\ or Varian!MAT 334 combined with Varian
2699 "14 m CP Sil 4 column#\ carrier gas He[ HRÐMS]
MAT 600 "69 eV#[ GC] Packard 328 with a 14 m CP Sil Scheme 1.
4 column "9[28 mm# and with a 59 m DB wax column
"9[14 mm#\ carrier gas N1\ RI  relative retention index[
IR "CCl3#] Perkin!Elmer 770[ Optical rotation] Perkin!
 Correspondence to] P[ Weyerstahl\ Institut fur Organische Chemie\ Tech!
Elmer polarimeter 030[ Split tube distillation] Fischer
nische Universitat Berlin\ Strasse des 06[ Juni 024\ D!09512 Berlin\ Germany[ HMS 299[ TLC] Silica gel 59 F143 "Merck No[ 4443#[

Copyright Þ 1999 John Wiley + Sons\ Ltd[

043 P[ WEYERSTAHL ET AL[

Table 1. Split-tube distillation of the methyl ether fraction VM

Fraction VM No[ b[p[ ">C#:9[91 mbar g Main "minor# constituents "GC] Sil 4# Further separation

0 32Ð34 9[5 M 1\ M 2\ M 3 FC 0
1 34 9[5 M 3\ M 5
2 35Ð37 0[4 M 3\ M 5\ M 6\ M 7 "M 09# FC 2
3 37Ð49 0[0 M 3\ M 5\ M 02\ M 03 "M 8\ M 01\ 05# FC 3
4 49 1[9 M 3\ M 5\ M 02\ M 03\ M 08\ "M 00# FC 4
5¦6 49Ð40 2[2 M 08\ M 10 FC 5
7¦8 41Ð43 1[8 M 08\ M 10\ M 29 "14)#
09Ð07 43Ð50 04[0 M 29 "39Ð89)#
08 50 0[4 M 18 "05)#\ M 29 "65)#a
19 50 0[3 M 18\ M 29 FC 19
10¦11 50 4[9 M 07\ M 13:M 14\ M 29 "04\ 06\ M 07\ M 15# FC 10
12 50 0[2 M 13:M 14 "42)#
13¦14 50Ð53 1[4 M 13:M 14\ 04 "M 20\ M 21\ M 28# FC 13
15¦16 53Ð54 2[2 M 30b
17 54Ð55 0[7 M 30b "22\ 23\ M 27\ M 30\ M 37# FC 17
18Ð21 55Ð56 4[9 M 30b "M 39\ M 31# FC 21
22Ð24 56Ð57 4[5 M 30\b 17 "11\ 12\ 16# FC 23
Residue 27[0 26\ alkylated b!vetivone derivatives
a
Percentage determined on a DB wax column[
b
VM 15Ð21] 36Ð51) M 30[

Flash chromatography "FC#] ICN Biomedicals silica
21!52 "if necessary\ impregnated with AgNO2# or
Florisilþ "099Ð199 mesh# or basic Al1O2\ 52Ð199 mm
"deactivated with 0Ð2) water#\ elution with light
petroleum ether "PE\ b[p[ 39Ð59>C# and increasing
amounts of Et1O[ For numbering "according to Con!
nolly4#\ see Schemes 1Ð7[ The compounds are presented
according to the schemes[
The methyl ether fraction VM "84 g# was prepared
from the medium polar to polar fraction V 2 "299 g\
main constituents] khusimol 29\ isonootkatol 39\ iso!
valencenol 30# as described in reference 0[ Split!tube
distillation "Fischer HMS 299 apparatus# at 32Ð
57>C:9[91 mbar gave the fractions shown in Table 0[
Fractions 0\ 2Ð5\ 19\ 10\ 17\ 21 and 23 were separated
by repeated FC on silica gel "SiO1#\ AgNO2 impregnated
silica gel "SiO1:AgNO2#\ alumina "Al1O2# or Florisilþ[
Only the main constituents of each fraction are given[
Bold letters show from which fraction the corresponding
methyl ether was isolated\ e[g[ M 09 was isolated from
fraction VM 2[0[
FC 1
FC "SiO1\ PE:4) Et1O# of VM 0 "9[5 g# gave VM 0[0\
9[12 g of M 3 "GC] 70)#\ VM 0[1\ 9[12 g\ M 1:M 2
"0 ] 0#[ Repeated FC "Re!FC^ 1×\ SiO1:AgNO2\ PE:3)
Et1O# of VM 0[1 gave VM 0[1[0\ 29 mg\ M 1 "GC] 42)#\
VM 0[1[1\ 099 mg\ M 2 "GC] 36)#[
FC 3
FC "Al1O2\ PE:1) Et1O# of VM 2 "0[4 g# gave VM 2[0\
34 mg\ M 09 "GC] 74)#\ VM 2[1\ 9[55 g\ M 3¦M 5\
VM 2[2\ 9[15 g\ M 5 "31)#\ M 6 "19)#\ VM 2[3\ 9[34
g\ M 7\ M 03\ M 08\ M 10[ Re!FC "1×\ SiO1:AgNO2\
PE:1) Et1O# of VM 2[2 gave VM 2[2[0\ 54 mg\ M 5
"GC] 54)#\ VM 2[2[1\ 14 mg\ M 6 "GC] 84)#[ Re!FC
"1×\ SiO1\ PE:3) Et1O# of VM 2[3 gave VM 2[3[0\ 29
mg\ M 10 "GC] 14)#\ VM 2[3[1\ 9[09 g\ M 08 "GC]
24)#\ VM 2[3[2\ 24 mg\ M 03 "19)#\ M 08 "19)#\ VM
2[3[3\ 034 mg\ M 7 "GC] 60)#[
FC 4
FC "SiO1\ PE:1) Et1O# of VM 3 "9[8 g# gave VM 3[0\
9[25 g\ M 3\ M 5\ M 09\ VM 3[1\ 9[19 g\ M 7\ M 01\ M
02\ M 03\ VM 3[2\ 9[22 g\ M 02\ M 03[ Re!FC "1×\
Al1O2\ PE# of VM 3[1 gave VM 3[1[0\ 15 mg\ M 1¦M
2 "11)#\ M 5 "05)#\ M 6 "30)#\ M 01 "03)#\ VM
3[1[1\ 19 mg\ M 6 "02)#\ M 01 "34)#\ M 29 "14)#[ Re!
FC "SiO1:AgNO2\ PE# of VM 3[2 gave VM 3[2[0\ 9[08
g\ VM 3[2[1\ 44 mg[ Re!FC "Al1O2\ PE# of VM 3[2[0
gave VM 3[2[0[0\ 59 mg\ M 02 "GC] 49)#\ 3[2[0[1\ 79
mg\ M 02 "19)#\ M 03 "39)#\ M 08 "19)#\ VM 3[2[0[2\
39 mg\ M 7[ Re!FC "SiO1\ PE\ 1Ð09) Et1O# of VM
3[2[1 gave VM 3[2[1[0\ 24 mg\ M 7\ VM 3[2[1[1\ 4 mg\
M 8 "GC] 79)#\ VM 3[2[1[2\ 2 mg\ 05 "GC] 74)#[
FC 5
FC "SiO1\ PE:4) Et1O# of VM 4 "0[7 g# gave VM 4[0\
9[04 g\ M 09 "GC] 40)#\ VM 4[1\ 9[20 g\ M 3¦M 5\
VM 4[2\ 9[45 g\ VM 4[3\ 9[55 g\ M 02\ M 03\ M 08[ Re!
FC "Al1O2\ PE# of VM 4[3 gave VM 4[3[0\ 9[09 g\ VM
4[3[1\ 9[29 g\ VM 4[3[2\ 9[07 g\ VM 4[3[3\ 19 mg\ M 00
"GC] 40)#[ Re!FC "SiO1:AgNO2\ PE\ 9Ð4) Et1O# of
VM 4[3[1 gave VM 4[3[1[0\ 59 mg\ M 08\ VM 4[3[1[1\
9[03 g\ M 02 "04)#\ M 03 "30)#\ M 08 "31)#\ VM
4[3[1[2\ 89 mg\ M 02[ Re!FC ð"a# SiO1:AgNO2\ PE:9Ð
3) Et1O^ "b# SiO1\ PE:9Ð3) Et1OŁ of VM 4[3[1[1 gave

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062

8 mg of M 03 "GC] 71)#[ Re!FC "Al1O2\ PE# of VM
4[3[3 gave 09 mg of M 00 "GC] 66)#[
FC 6
FC "SiO1\ PE:4) Et1O# of VM 5 "9[85 g# gave VM 5[0\
9[09 g\ M 3¦M 5\ VM 5[1\ 9[13 g M 10 "GC] 14)#\
VM 5[2\ 9[16 g\ M 08 "GC] 65)#\ M 02 "19)#\ VM 5[3\
9[29 g\ M 03\ M 08[
FC 20
FC "Al1O2\ PE# of VM 19 "0[1 g# gave VM 19[0\ 9[49 g\
M 29\ VM 19[1\ 9[42 g\ M 18\ M 29\ VM 19[2\ 9[19 g\
M 07\ M 18\ M 29[ Re!FC "1×\ Al1O2:PE# of VM 19[2
gave 29 mg of M 18 "GC] 79)#[
FC 21
FC "SiO1\ PE:1Ð4) Et1O# of VM 10 "2[1 g# gave VM
10[0\ 39 mg\ M 15 "GC] 89)#\ VM 10[1\ 9[55 g\ M 29\
"GC] 84)#\ VM 10[2\ 0[2 g\ M 13:M 29 "0 ] 0#\ VM 10[3\
9[54 g\ M 13 "GC] 64)#\ M 14 "GC] 02)#\ VM 10[4\
9[15 g\ M 07\ M 13\ 04\ 06[ Re!FC "1×\ SiO1\ PE:9Ð
4) Et1O# of VM 10[4 gave VM 10[4[0\ 9[09 g\ M 13:M
14\ VM 10[4[1\ 29 mg\ M 07 "43)#\ VM 10[4[2\ 19 mg\
06 "GC] 54)#\ VM 10[4[3\ 9[09 g\ 04 "GC] 72)#[
FC 24
FC "SiO1\ PE:9Ð4) Et1O# of VM 13 "0[1 g# gave VM
13[0\ 9[03 g\ VM 13[1\ 9[37 g\ VM 13[2\ 9[02 g\ VM
13[3\ 9[32 g\ 04 "GC] 65)#[ Re!FC "1×\ SiO1:AgNO2\
PE:9Ð4) Et1O# of VM 13[0 gave VM 13[0[0\ 19 mg\ M
28 "GC] 81)#\ VM 13[0[1\ 89 mg\ M 13:M 14[ Re!FC
"1×\ SiO1\ PE:9Ð4) Et1O# of VM 13[2 gave VM 13[2[0\
4 mg\ M 21 "GC] 76)#\ VM 13[2[1\ 3 mg\ M 20 "GC]
26)#\ M 30 "24)#^ VM 13[2[2\ 2 mg M 20\ M 30[
FC 28
FC "SiO1\ PE:9Ð19) Et1O# of VM 17 "0[7 g# gave VM
17[0\ 9[04 g\ M 32 "GC] 89)#\ VM 17[1\ 9[09 g\ M 13:M
14 "34)#\ VM 17[2\ 9[26 g\ M 13 "01)#\ M 30 "56)#\
VM 17[3\ 9[24\ M 30 "GC] 87)#\ VM 17[4\ 9[47 g\ M
27 "09)#\ M 30 "59)#[ Re!FC "SiO1# of VM 17[4 gave
VM 17[4[0\ 9[32 g\ M 27 "01)#\ M 30 "66)#\ VM
17[4[1\ 9[04 g[ Re!FC "1×\ SiO1# of VM 17[4[0 gave
VM 17[4[0[0\ 9[15 g\ M 30 "GC] 86)#\ VM 17[4[0[1\
39 mg\ M 27 "GC] 70)#[ Re!FC "2×\ SiO1:AgNO2\
PE:Et1O\ 5 ] 3# of VM 17[4[1 gave VM 17[4[1[0\ 6 mg\
23 "GC] 56)#\ VM 17[4[1[1\ 04 mg\ 22 "GC] 63)#[
Copyright Þ 1999 John Wiley + Sons\ Ltd[
POLAR FRACTION OF HAITIAN VETIVER OIL 044
FC 32
FC "SiO1# of VM 21 "0[7 g# gave VM 21[0\ 9[25 g\ VM
21[1\ 9[30 g\ M 30:M 31 "3 ] 0#\ VM 21[2\ 9[10 g\ VM
21[3\ 9[11 g[ Re!FC ð"a# SiO1^ "b# SiO1:AgNO2\ PE:2)
Et1OŁ of VM 21[1 "49 mg# gave 6 mg\ M 31 "GC] 44)#\
M 30 "24)#[ Re!FC "SiO1# of VM 21[2 gave 9[05 g\ M
39 "GC] 72)#[
FC 34
FC "1×\ SiO1# of VM 23 "9[2 g# gave VM 23[0\ 39 mg\
12 "GC] 47)#\ 16 "GC] 22)#\ VM 23[1\ 19 mg\ 11 "GC]
89)#\ VM 23[2\ 89 mg\ 17 "GC] 74)#[
Eudesma-4(15),7-dien-3b
b -yl methyl ether (M 7)
RI "wax#] 0747[ ðaŁD¦3> "c 0[5\ CHCl2^ GC] 84)#[ 0H!
NMR "with NOED#] d 9[57 "s\ 09!Me#\ 0[91 "d\ J  6
Hz\ 00!Me1#\ 0[17 "ddd\ J  02[4\ 3\ 2 Hz\ 0!Heq#\ 0[69
"mc\ 0!Hax#\ 0[72 "dddd\ J  03\ 03\ 4\ 2 Hz\ 1!Hax#\ 0[85
"dd\ br[\ J  04\ 00[4 Hz\ 5!Hax#\ 1[10 "sept[\ br[\ J  6
Hz\ 00!H#\ 1[17 "dddd\ J  00[4\ 4\ 1\ 0[4 Hz\ 4!Hax#\
2[07 "s\ OMe#\ 2[69 "dd\ J  2\ 2 Hz\ 2!Heq#\ 3[73 "dd\
J  1\ 1 Hz# and 3[88 "dd\ J  1\ 0[4 Hz\ 3!CH1#\ 4[29
"d\ br[\ J  4 Hz\ 7!H#[ 02C!NMR] see Table 2[ GCÐ
MS "HP#] m:z ")# 123 "M¦\ 10#\ 108 "5#\ 191 "39#\ 076
"21#\ 065 "05#\ 050 "15#\ 048 "099#\ 036 "15#\ 034 "33#\
027 "49#\ 022 "23#\ 020 "52#\ 008 "36#\ 006 "33#\ 096 "31#\
095 "31#\ 094 "62#\ 82 "24#\ 80 "70#\ 68 "23#\ 66 "22#\ 56
"15#\ 44 "15#[ C05H15O] calcd[ 123[0873\ found 123[0874
"HRÐMS#[
Eudesma-4(15),7-dien-3b b -ol (7), prepared by
saponification of a fraction isolated from
commercial vetiveryl acetate
GC] 44)[ RI "Sil 4#] 0527[ 0H!NMR] d 9[56 "s\ 09!Me#\
0[91 "d\ J  6 Hz\ 00!Me1#\ 0[17 "mc\ 0!Heq#\ 0[52 "mc\ 0
H#\ 0[67 "mc\ 0 H#\ 0[76 "mc\ 1 H#\ 0[80 "mc\ 0 H#\ 0[88
"mc\ 1 H#\ 1[10 "sept[\ br[\ J  6 Hz\ 00!H#\ 1[37 "dddd\
J  00\ 4\ 1\ 0[4 Hz\ 4!Hax#\ 3[23 "dd\ br[\ J  2\ 2 Hz\
2!Heq#\ 3[62 "dd\ J  1\ 1 Hz# and 4[92 "dd\ J  1\ 0[4
Hz\ 3!CH1#\ 4[20 "d\ br[\ J  4 Hz\ 7!H#[ GCÐMS
"MAT#] m:z ")# 119 "M¦\ 06#\ 191 "08#\ 076 "07#\ 066
"06#\ 048 "59#\ 034 "29#\ 022 "17#\ 020 "41#\ 008 "44#\ 006
"36#\ 096 "35#\ 095 "35#\ 094 "79#\ 84 "14#\ 82 "42#\ 80
"099#\ 70 "27#\ 68 "40#\ 66 "32#\ 56 "49#\ 44 "49#\ 42 "21#[
Eudesma-4(15),7-dien-2bb -yl methyl ether
(isovetiselinenyl methyl ether, M 18)
GC] 43)[ 0H!NMR "with NOED#] d 9[56 "s\ 09!Me#\
0[90\ 0[904 "1 d\ J  4 Hz\ 00!Me1#\ 0[07 "dd\ J  01\ 01
Hz\ 0!Hax#\ 0[61 "mc\ 4!H\ 5!Heq#\ 0[76 "dd\ br[\ J  05\
4 Hz\ 8!Heq#\ 0[83 "mc\ 0!Heq\ 2!Hax\ 5!Hax\ 8!Hax#\ 1[19
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
045 P[ WEYERSTAHL ET AL[

Table 2. Constituents of the methyl ether fraction VM prepared from the polar vetiver oil fraction V 3 (all
compounds were identified by their 1H-, 13C-NMR and MS data)a
No[ Scheme Compound ")# RRI Reference
Sil 4

M 0 n[i[ 0[0 0430

M 1 5 01!nor!Ziza!5"02#!en!1b!yl methyl ether 0[0 0441
M 2 5 01!nor!Ziza!5"02#!en!1a!yl methyl ether 9[7 0456
M 3 0 Cyclocopacamphan!01!yl methyl ether A 1[3 0461 0
4 n[i[ 9[5 0468
M 5 0 Cyclocopacamphan!01!yl methyl ether B 2[2 0472 0
M 6 1 Eudesma!3"04#\6!dien!2b!yl methyl ether 0[5 ~0475
M 7 4 6\09!Epoxy!09!methoxysalvialane _0475
M 8 0 3a\6!Epoxy!00!methoxy!09bH!spirovetiv!1!ene 9[2 0484 1
M 09 6 Khusian!1!yl methyl ether 9[2 ~0599
M 00 3 Guaia!0"4#\00!dien!2a!yl methyl ether _0599
M 01 6 Helifolen!03!yl methyl ether "khusien!03!yl methyl ether# F0502
M 02 0 b!Funebren!03!yl methyl ether 3[9 j0502 0
M 03 5 Preziza!6"04#!en!2a!yl methyl ether J0502
04 00 Eudesm!5!en!3b!ol f0502 28Ð30
05 09 ð00\01\02!tri!nor!7\7!Dimethyleudesm!4!en!6!oneŁ 9[1 0519
06 09 ð00\01\02!tri!nor!7\7!Dimethyleudesma!2\4!dien!6!oneŁ F0515
M 07 1 Eudesma!3"04#\6!dien!1b!yl methyl ether g0515
M 08 5 Ziza!5"02#!en!2a!yl methyl ether 3[8 f0515
M 19 n[i[ 9[6 0522
M 10 5 Ziza!5"02#!en!2b!yl methyl ether 1[8 F0539
11 00 b!Eudesmolb\c g0539
12 00 Valerianolb f0539
M 13 1 Eudesma!3"04#\6!dien!01!yl methyl ether 5[3 F0534
M 14 1 00!epi!Eudesma!3"04#\6!dien!01!yl methyl ether G0534
M 15 1 Eudesma!2\4!dien!0a!yl methyl ether g0534
16 00 a!Eudesmol G0534
f0534
17 00 Amorph!3!en!09!olb\d 3
M 18 0 Preziza!6"04#!en!01!yl methyl ether F0549 0
M 29 0 Ziza!5"02#!en!01!yl methyl ether "khusimyl methyl ether# 22[9 g0549 0
M 20 2 6aH!Eremophila!0"09#\3"04#!dien!1a!yl methyl ether f0549
M 21 0 3bH!cis!Eudesma!5\00!dien!2b!yl methyl ether 0[7 F0543 2
22 3 3aH\4aH\6aH!Guai!00!en!09a!ol "pogostol# g0543
23 00 Eudesm!00!en!3b!ol "intermedeol#e f0543 31\32
M 24 n[i[ "1 Compounds\ M¦  123\ 125# 0[3 0556
M 25 n[i[ 9[5 0561
26 00 Eudesm!6"00#!en!3b!ol "juniper camphor#f 9[2 0579 33
M 27 1 6aH!Eremophila!0"09#\00!dien!1a!yl methyl ether 0[6 0575
M 28 8 ð1!Methoxyspirovetiva!1\3"04#\6"00#!trieneŁ 9[4 0582
M 39 1 Eremophila!0"09#\6"00#!dien!1a!yl methyl ether 9[8 0604
M 30 1 "E#!Eremophila!0"09#\6"00#!dien!01!yl methyl ether 5[6 ~0617
M 31 7 Spirovetiva!2\6"00#!dien!01!yl methyl ether _0617
M 32 8 ð1!Methoxy!2\2!dimethylspirovetiva!0\3"04#\6"00#!trieneŁ 9[8 ~0639
5\01^6\00!Di!epoxy!eudesm!3!ene "epimer A# _0639 36
5\01^6\00!Di!epoxy!eudesm!3!ene "epimer B# 9[3 ~0642 36
6\00^7\01!Di!epoxy!eremophil!8!ene "epimer A# _0642 36
6\00^7\01!Di!epoxy!eremophil!8!ene "epimer B# 9[1 0683 36
n[i[\ not identi_ed[
a
Compounds in square brackets are artefacts formed by reaction of ketones "i[e[ b!vetivone 41# with MeI[
b
Compounds previously identi_ed in vetiver oil[
c
ðaŁD ¦37> "c 5\ CHCl2\ GC] 84)#^ reference 7] ðaŁD ¦50>[
d
ðaŁD ¦13[2> "c 23\ CHCl2\ GC] 82)#\ m[p[ 39>C^ reference 34 "17 was obtained on treatment of "¦#!a!ylangene with diluted mineral acid#] ðaŁD −7[6> "c
9[4\ CHCl2#\ m[p[ 31>C[
e
ðaŁD ¦02> "c 7\ CHCl2\ GC] 56)#^ reference 31] ðaŁD ¦07> "c 1[7\ CHCl2#\ 23 was obtained by hydrolysis of the corresponding glycoside isolated from
Carthamus lanatus[
f
ðaŁD ¦6> "c 21\ CHCl2\ GC] 74)#^ reference 33] ðaŁD ¦3> "c 9[4\ MeOH#\ 26 was isolated from La``era pterodonta[

"sept[\ br[\ J  6 Hz\ 00!H#\ 1[66 "ddd\ J  01\ 4\ 1 Hz\
2!Heq#\ 2[21 "dddd\ J  01\ 4\ 3\ 2 Hz\ 1!Hax#\ 2[24 "s\
OMe#\ 3[57\ 3[78 "1 ddd\ J  0[4\ 0[4\ 0[4 Hz\ 3!CH1#\
4[18 "dd\ br[\ J  4\ 0[4 Hz\ 7!H#[ Values "59 MHz# of
isovetiselinenol 075 for comparison] d 9[55 "s#\ 0[90 "d\
J  6 Hz\ 00!Me1#\ 0[80 "s\ br[\ 5 H#\ 1[0Ð1[55 "m\ 1H#\
2[64 "m\ CHOH#\ 3[54\ 3[74 "1 s#\ 4[14 "s\ br[#[ 02C!
NMR] see Table 2[ GCÐMS "HP#] m:z ")# 123 "M¦\
24#\ 108 "1#\ 191 "08#\ 076 "24#\ 062 "4#\ 048 "099#\ 034
"21#\ 020 "20#\ 008 "20#\ 006 "21#\ 094 "26#\ 82 "13#\ 80
"23#\ 68 "10#\ 66 "08#[ C05H15O] calcd[ 123[0873\ found
123[0880 "HRÐMS#[

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
 POLAR FRACTION OF HAITIAN VETIVER OIL 046

Table 3. 13C-NMR data (d, CDCl3) of the eudesmadiene derivatives M 7, M 18, M 24, M 25, M 26 and (for
comparison) vetiselinenol 24 (for numbering, see Scheme 2)
C!No[ M6 M 07 13a M 13 M 14 M 15
0 t 30[5 t 36[9 t 30[4 30[5 30[5 d 73[8
1 t 14[4 d 65[3 t 12[4 12[5 12[5 t 17[1
2 d 71[3 t 32[9 t 26[0 26[1 26[1 d 010[0
3 s 037[5 s 036[4 s 049[0 049[2 049[3 s 031[0
4 d 28[6 d 33[3 d 33[6 33[7 33[7 s 021[9
5 t 17[6 t 14[7 t 14[1 14[7 15[0 d 014[6
6 s 030[8 s 031[0 s 026[3 027[1 027[0 d 31[3
7 d 005[4 d 005[0 d 010[9 008[1 008[3 t 19[4
8 t 24[3 t 30[7 t 30[8 30[8 30[8 t 23[0
09 s 23[1 s 22[7 s 23[4 23[4 23[4 s 26[8
00 d 24[0 d 24[9 d 32[4 39[8 30[9 d 21[3
3!CH1 t 009[8 t 097[6 t 095[2 095[0 095[0 3!Me q 07[8
09!Me q 05[6 q 07[9 q 06[1 06[9 06[0 q 06[4
00!Me q 10[2 q 10[2 q 04[7 05[5 05[2 q 08[5
00!Me q 10[6 q 10[6 00!CH1 t 54[4 65[6 66[9 00!Me q 08[8
OMe q 44[1 q 44[6 q 47[5 47[5 q 46[2
a
With 0H02C!correlation[

Eudesma-4(15),7-dien-12-yl methyl ether
(vetiselinenyl methyl ether M 24, GC: 80%, with
20% of 11-epi-Eudesma-4(15),7-dien-12-yl methyl
ether, M 25)
M 13] RI "wax#] 0884^ M 14] RI "wax# 1999[ ðaŁD −03[8>
"c 5[4\ CHCl2#^ for comparison ðaŁD of 13] −07[0> "ref!
erence 6#^ −11> "reference 7#[ 0H!NMR "with NOED^
M 13^ M 14\ if di}erent#] d 9[57:9[56 "s\ 09!Me#\
0[91:0[92 "d\ J  6 Hz\ 00!Me#\ 0[29 "ddd\ J  02[4\
02[4\ 2 Hz\ 0!Hax#\ 0[40 "dddd\ J  02[4\ 02\ 3\ 2 Hz\ 1!
Hax#\ 0[44 "mc\ 0!Heq#\ 0[59 "mc\ 1!Heq#\ 0[71 "dd\ br[\
J  05[4\ 4 Hz\ 8!Heq#\ 0[80 "mc\ 5!H1#\ 0[82:0[75 "mc\ 8!
Hax#\ 0[86:0[89 "dddd\ J  02[4\ 6[4\ 0[4\ 0 Hz\ 4!Hax#\
1[99 "dd\ br[\ J  02[4\ 4 Hz\ 2!Hax#\ 1[24 "dddd\
J  02[4\ 3\ 1\ 1 Hz\ 2!Heq#\ 1[27 "ddq\ J  6\ 6\ 6 Hz\
00!H#\ 2[12:2[11 and 2[27:2[28 "1 dd\ J  8\ 6 Hz\ 01!
H1#\ 2[22 "s\ OMe#\ 3[45\ 3[67 "1 ddd\ J  1\ 0[4\ 0 Hz\
3!CH1#\ 4[25:4[26 "d\ br[\ J  4 Hz\ 7!H#[ Values of
vetiselinenol 136 for comparison] d 9[69 "s#\ 0[92 "d\
J  5[5 Hz#\ 2[34\ 2[46 "1 s\ br[#\ 3[46\ 3[67 "1 s#\ 4[33 "t\
br[#[ 02C!NMR] see Table 2[ GCÐMS "HP#] m:z ")#
123 "M¦\ 7#\ 191 "099#\ 078 "52#\ 076 "42#\ 062 "12#\ 050
"20#\ 048 "08#\ 036 "08#\ 034 "15#\ 022 "33#\ 020 "16#\ 006
"05#\ 096 "13#\ 094 "39#\ 84 "18#\ 82 "10#\ 80 "28#\ 68 "10#\
66 "05#[ C05H15O] calcd[ 123[0873\ found 123[0873 "HRÐ
MS#[
Odour of M 13 "GC] 79)#] warm woody\ khus!
imone!\ vetiver!like[ Odour of 13 "GC] 79)#] woody\
vetiver!\ cedar!\ ambra!like[
Eudesma-3,5-dien-1aa-yl methyl ether (M 26)
RI "wax#] 0856[ ðaŁD ¦13> "c 9[2\ CHCl2^ GC] 89)#[
0
H!NMR "with NOED#] d 9[78\ 9[82 "1 d\ J  6 Hz\ 00!
Me1#\ 9[80 "s\ 09!Me#\ 0[18 "ddd\ J  02\ 02\ 2 Hz\ 8!
Hax#\ 0[30 "dddd\ J  02\ 02\ 00\ 2 Hz\ 7!Hax#\ 0[52 "ddd\
J  02\ 2\ 2 Hz\ 8!Heq#\ 0[57 "qqd\ J  6\ 6\ 4 Hz\ 00!
H#\ 0[66 "dddd\ J  1\ 1\ 1\ 0[4 Hz\ 3!Me#\ 0[86 "ddd\
J  02\ 2\ 2 Hz\ 7!Heq#\ 1[93 "ddd\ br[\ J  07\ 09\ 2 Hz\
1!Hax#\ 1[97 "dd\ br[\ J  00\ 2 Hz\ 6!Hax#\ 1[37 "ddd\
br[\ J  07\ 5\ 4 Hz\ 1!Heq#\ 2[90 "dd\ J  09\ 5 Hz\ 0!
Hax#\ 2[25 "s\ OMe#\ 4[30 "d\ br[\ J  4 Hz\ 2!H#\ 4[38
"d\ br[\ J  0[4 Hz\ 5!H#[ Values of eudesma!2\4!dien!0!
ol 158 for comparison] d 9[78\ 9[82 "1 d#\ 9[80 "s#\ 2[40
"dd\ 0!Hax#^ 4[39 "dq#\ 4[41 "d#[ 02C!NMR] see Table 2[
GCÐMS "HP#] m:z ")# 123 "M¦\ 15#\ 108 "1#\ 191 "02#\
080 "39#\ 048 "099#\ 034 "02#\ 020 "18#\ 006 "35#\ 094 "12#\
80 "13#\ 70 "04#\ 66 "03#\ 56 "09#\ 44 "09#[ C05H15O] calcd[
123[0873\ found 123[0875 "HRÐMS#[
Odour of M 15 "GC] 89)#] vetiver!\ rhubarb!\ grape!
fruit!like[
7aaH-Eremophila-1(10),4(15)-dien-2aa-yl methyl
ether (M 31)
GC] 26)\ mixture with 24) of M 30[ 0H!NMR "with
NOED#] d 9[76\ 9[78 "1 d\ J  5[4 Hz\ 00!Me1#\ 0[12 "s\
4!Me#\ 0[39 "mc\ 00!H#\ 0[79 "ddd\ J  01[4\ 2\ 1[4 Hz\
5!Heq#\ 1[00 "ddd\ J  03\ 3\ 1[4 Hz\ 8!Heq#\ 1[25 "ddd\
J  01\ 09\ 0[4 Hz\ 2!Hax#\ 1[51 "ddd\ J  01\ 4[4\ 0[4
Hz\ 2!Heq#\ 2[26 "s\ OMe#\ 2[68 "dddd\ J  09\ 4[4\ 1\ 1
Hz\ 1!Hax#\ 3[79 "d\ br[\ J  0[4 Hz\ 3!CH1#\ 4[32 "d\ br[\
J  1 Hz\ 0!H#[ 02C!NMR] see Table 3[ GCÐMS "HP#]
m:z ")# 123 "M¦\ 4#\ 108 "02#\ 191 "39#\ 076 "08#\ 059
"04#\ 048 "099#\ 034 "15#\ 022 "07#\ 021 "21#\ 020 "55#\
018 "08#\ 017 "12#\ 008 "16#\ 007 "12#\ 006 "23#\ 004 "13#\
094 "13#\ 80 "23#\ 66 "04#[ C05H15O] calcd[ 123[0873\
found 123[0881 "HRÐMS#[
7aaH-Eremophila-1(10),11-dien-2aa-yl methyl ether
(nootkatyl methyl ether, M 38)
GC] 70) 0H!NMR "with COSY and NOED#] d 9[78
"d\ J  6 Hz\ 3!Me#\ 9[83 "dd\ J  02\ 02 Hz\ 5!Hax#\

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
047 P[ WEYERSTAHL ET AL[

Table 4. 13C-NMR data (d, CDCl3) of the eremophiladiene derivatives M 31, M 38, M 40, M 41 and (for comparison)
nootkat-2b-ol A, isonootkatol 40 and isovalencenol 41 (for numbering, see Scheme 3)
C!No[ M 20 M 27a Ab M 39a 39a M 30a 30
0 d 010[0 d 010[3 010[6 d 019[8 012[7 d 008[8 019[0
1 d 60[5 d 65[3 53[3 d 65[3 57[9 t 14[6 14[7
2 t 25[6 t 22[9 25[1 t 22[4 26[5 t 16[2 16[2
3 s 059[6 d 28[0 24[9 d 27[1 27[3 d 39[9 39[0
4 s 33[1c s 27[2 27[2 s 39[8 39[6 s 39[4 39[5
5 t 30[9 t 33[5 33[5 t 31[0 31[0 t 31[5 31[5
6 d 28[2 d 39[6 39[6 s 017[7 017[6 s 024[7 024[1
7 t 29[5 t 21[8 21[5 t 20[1 20[1 t 20[0 20[0
8 t 21[0 t 21[3 21[4 t 22[3 22[3 t 23[9 23[1
09 s 042[4 s 035[3 037[5 s 036[9 035[5 s 031[8 032[9
00 d 21[6 s 049[1 049[0 s 011[7 011[8 s 012[6 015[3
3!CH1 t 096[4 3!Me q 04[4 04[1 3!Me q 04[7 04[5 q 04[7 04[8
4!Me q 14[7 4!Me q 07[0 05[7 4!Me q 06[1 06[2 q 06[3 06[3
00!Me q 08[4 00!Me q 19[7 19[7 00!Me q 19[9 19[0 q 05[2 05[3
00!Me q 19[9 00!CH1 t 097[4 097[6 00!Me q 19[0 19[1 t 61[4 52[4
1!OMe q 44[4 1!OMe q 44[3 1!OMe q 44[2 q 46[0
a
With 0H02C!correlation[
b
Some assignments given in reference 00 are changed according to the COSY!spectrum of M 27[
c
Presumably\ intensity very low[

9[87 "s\ 4!Me#\ 0[08 "dddd\ J  03\ 02\ 02\ 2 Hz\ 7!Hax#\
0[25 "ddd\ J  02\ 01\ 09 Hz\ 2!Hax#\ 0[37 "dqd\ J  02\
6\ 1 Hz\ 3!Hax#\ 0[69 "s\ br[\ 00!Me#\ 0[67 "d\ br[\ J  02
Hz\ 7!Heq#\ 0[68 "dddd\ J  01\ 5\ 1\ 1 Hz\ 2!Heq#\ 0[74
"ddd\ J  02\ 2\ 1 Hz\ 5!Heq#\ 1[00 "ddd\ J  03\ 3\ 2 Hz\
8!Heq#\ 1[12 "dddd\ J  02\ 02\ 2\ 2 Hz\ 6!Hax#\ 1[22
"ddddd\ J  03\ 03\ 3\ 2\ 1 Hz\ 8!Hax#\ 2[24 "s\ OMe#\
2[72 "dddd\ J  09\ 5\ 1\ 1 Hz\ 1!Hax#\ 3[56 "s\ br[\ 00!
CH1#\ 4[26 "ddd\ J  1\ 1\ 1 Hz\ 0!H#[ Values of noot!
katol 27 "RI] Sil 4 0699#\ prepared by NaBH3 reduction
of nootkatone\ for comparison] d 9[78 "d#\ 9[84 "dd#\
0[99 "s#\ 0[60 "s#\ 3[14 "dddd#\ 3[57 "s\ br[#\ 4[20 "ddd#\
all other values and couplings J as given for M 27[ 02C!
NMR] see Table 3[ GCÐMS "HP#] m:z ")# 123 "M¦\
2#\ 108 "1#\ 191 "21#\ 076 "05#\ 050 "28#\ 048 "13#\ 034
"28#\ 020 "39#\ 008 "099#\ 094 "34#\ 80 "41#\ 66 "13#\ 54
"00#\ 42 "00#[ C05H15O] calcd[ 123[0873\ found 123[0876
"HRÐMS#[
Odour of M 27 "GC] 70)#] vetiver!\ grapefruit!like\
dusty[
Eremophila-1(10),7(11)-dien-2aa-yl methyl ether
(isonootkatyl methyl ether, M 40)
GC] 72)[ 0H!NMR "with COSY and NOED#] d 9[72
"s\ 4!Me#\ 9[83 "d\ J  6 Hz\ 3!Me#\ 0[23 "ddd\ J  02\
02\ 09 Hz\ 2!Hax#\ 0[27 "d\ br[\ J  02 Hz\ 5!Hax#\ 0[45
"dqd\ J  02\ 6\ 1 Hz\ 3!Hax#\ 0[56 "s\ br[\ 00!Me#\ 0[56
"ddd\ br[\ J  02\ 02\ 4 Hz\ 7!Hax#\ 0[69 "d\ J  0 Hz\
00!Me#\ 0[70 "dddd\ J  02\ 5\ 1\ 1 Hz\ 2!Heq#\ 1[01
"ddd\ J  03\ 4\ 1[4 Hz\ 8!Heq#\ 1[13 "ddddd\ J  03\ 02\
4\ 1[4\ 1 Hz\ 8!Hax#\ 1[60 "dddd\ J  02\ 4\ 1[4\ 1 Hz\ 7!
Heq#\ 1[67 "dd\ J  02\ 1[4 Hz\ 5!Heq#\ 2[25 "s\ OMe#\
2[76 "dddd\ J  09\ 5\ 1\ 1 Hz\ 1!Hax#\ 4[26 "ddd\ J  1\
1\ 1 Hz\ 0!H#[ 02C!NMR] see Table 3[ GCÐMS "HP#]
m:z ")# 123 "M¦\ 1#\ 108 "9[4#\ 192 "07#\ 191 "099#\ 076
"39#\ 048 "71#\ 034 "66#\ 032 "10#\ 020 "42#\ 018 "13#\ 017
"18#\ 008 "26#\ 006 "21#\ 004 "15#\ 096 "10#\ 094 "18#\ 84
"05#\ 80 "26#\ 66 "07#[ C05H15O] calcd[ 123[0873\ found
123[0875 "HRÐMS#[
Odour of M 39 "GC] 72)#] weak[
Isolation of isonootkatol (40) from fraction V 3
FC "SiO1\ PE:Et1O 0 ] 0# of the polar fraction V 2 "03 g#
yielded V 2[0\ 9[3 g\ 30\ V 2[1\ 02 g\ 29 and 30\ V 2[2\
9[4 g\ 39 and 30[ Re!FC of V 2[2 gave 39 "9[03 g#\ which
decomposed easily[ Isonootkatol "39#[ RI "Sil 4#] 0624[
GC] 59)[ 0H!NMR "with COSY and NOED#] d 9[73
"s\ 4!Me#\ 9[82 "d\ J  6 Hz\ 3!Me#\ 0[23 "ddd\ J  02\
01\ 01 Hz\ 2!Hax#\ 0[27 "d\ br[\ J  02 Hz\ 5!Hax#\ 0[46
"dqd\ J  02\ 6\ 1 Hz\ 3!Hax#\ 0[56 "s\ br[\ 00!Me#\ 0[58
"ddd\ br[\ J  03\ 02[4\ 1 Hz\ 7!Hax#\ 0[69 "d\ J  0 Hz\
00!Me#\ 0[79 "dddd\ J  01\ 5[4\ 1\ 1 Hz\ 2!Heq#\ 1[00
"ddd\ J  03\ 3[4\ 1[4 Hz\ 8!Heq#\ 1[12 "dddd\ J  03\
03\ 4\ 1 Hz\ 8!Hax#\ 1[61 "dddd\ J  02[4\ 4\ 1[4\ 1 Hz\
7!Heq#\ 1[67 "dd\ J  02\ 1[4 Hz\ 5!Heq#\ 3[16 "dddd\
J  01\ 5[4\ 1\ 1 Hz\ 1!Hax#\ 4[20 "ddd\ J  1\ 1\ 1 Hz\
0!H#[ 02C!NMR] see Table 3[
MnO2 oxidation of 40
Isonootkatone "a!vetivone\ B#
RI "Sil 4#] 0702[ GC] 65)[ Obtained by MnO1 oxidation
of 39[ 0H!NMR] d 9[84 "s\ 4!Me#\ 9[88 "d\ J  6 Hz\ 3!
Me#\ 0[53 "d\ br[\ J  02[4 Hz\ 5!Hax#\ 0[69\ 0[61 "1 dd\
J  0\ 0 Hz\ 00!Me1#\ 0[76 "dd\ br[\ J  04\ 02[4 Hz\ 7!
Hax#\ 1[94 "dqd\ J  03\ 6\ 3 Hz\ 3!Hax#\ 1[11 "dd\ J  06\
3 Hz\ 2!Heq#\ 1[15 "dd\ J  06\ 03 Hz\ 2!Hax#\ 1[24 "ddd\
J  04\ 5\ 1[4 Hz\ 8!Heq#\ 1[30 "dddd\ J  04\ 04\ 4[4\ 1
Hz\ 8!Hax#\ 1[64 "dddd\ J  02[4\ 4\ 1[4\ 1[4 Hz\ 7!Heq#\
1[67 "dd\ J  02[4\ 1 Hz\ 5!Heq#\ 4[63 "d\ J  0[4 Hz\ 0!

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062

H#^ reference 09] d 9[80 "s#\ 9[81 "d\ J  5 Hz#\ 0[69 "s\
br[\ 00!Me1#\ 4[67 "s\ br[#[ 02C!NMR] d 04[0 "q\ 3!Me#\
05[3 "q\ 4!Me#\ 19[0\ 19[04 "1 q\ 00!Me1#\ 18[8 "t\ C!7#\
22[6 "t\ C!8#\ 28[1 "d\ C!3#\ 39[7 "t\ C!2#\ 30[6 "s\ C!4#\
31[2 "t\ C!5#\ 013[1 "d\ C!0#\ 013[6 "s\ C!00#\ 015[7 "s\ C!
6#\ 060[4 "s\ C!09#\ 088[5 "s\ C!1#[ GCÐMS "MAT#] m:z
")# 107 "M¦\ 49#\ 192 "08#\ 074 "099#\ 050 "25#\ 046
"12#\ 036 "42#\ 022 "24#\ 010 "44#\ 008 "25#\ 094 "42#\ 82
"16#\ 80 "55#\ 68 "24#\ 66 "25#\ 58 "15#\ 56 "26#\ 54 "12#\
44 "34#\ 42 "15#[
Odour of isonootkatone "B\ GC] 65)#] bitter\ strong
grapefruit!like\ tenacious[
E-Eremophila-1(10),7(11)-dien-12-yl methyl ether
(isovalencenyl methyl ether, M 41)
RI "wax#] 1001[ ðaŁD ¦099[1> "c 00\ CHCl2\ GC] 88)#[
0 08#\ 191 "31#\ 076 "21#\ 048 "71#\ 036 "18#\ 035 "23#\ 034
H!NMR "with COSY and NOED#] d 9[72 "s\ 4!Me#\
9[82 "d\ J  5[4 Hz\ 3!Me#\ 0[28 "dddd\ J  00\ 5\ 4\ 2
Hz\ 2!Heq#\ 0[32 "dddd\ J  00\ 00\ 6\ 4 Hz\ 2!Hax#\ 0[38
"d\ br[\ J  02 Hz\ 5!Hax#\ 0[42 "dqd\ J  6\ 5[4\ 2 Hz\
3!Hax#\ 0[63 "dddd\ J  02\ 02\ 4\ 2 Hz\ 7!Hax#\ 0[64 "dd\
J  0\ 0 Hz\ 00!Me#\ 0[84 "ddddd\ J  07\ 4\ 4\ 2\ 1 Hz\
1!Heq#\ 1[94 "dddd\ J  07\ 00\ 5\ 2 Hz\ 1!Hax#\ 1[03
"ddd\ J  03\ 4\ 1[4 Hz\ 8!Heq#\ 1[14 "dddddd\ J  03\
02\ 4\ 2\ 2\ 1 Hz\ 8!Hax#\ 1[67 "dddd\ J  02\ 4\ 1[4\ 1[4
Hz\ 7!Heq#\ 1[71 "dd\ J  02\ 1[4 Hz\ 5!Heq#\ 2[18 "s[
OMe#\ 2[86 "dq\ J  00\ 0 Hz# and 2[88 "d\ J  00 Hz\
00!CH1O#\ 4[22 "ddd\ J  4\ 2\ 2 Hz\ 0!H#[ 02C!NMR]
see Table 3[ GCÐMS "HP#] m:z ")# 123 "M¦\ 1#\ 108
"1#\ 192 "07#\ 191 "099#\ 078 "09#\ 077 "00#\ 076 "62#\ 062
"09#\ 050 "07#\ 059 "26#\ 048 "42#\ 034 "60#\ 022 "07#\ 021
"13#\ 020 "45#\ 018 "07#\ 017 "08#\ 008 "20#\ 006 "28#\ 004
"13#\ 096 "07#\ 094 "36#\ 84 "02#\ 82 "12#\ 80 "42#\ 70 "05#\
68 "13#\ 66 "18#\ 56 "09#\ 54 "02#\ 44 "04#\ 42 "04#[
C05H15O] calcd[ 123[0873\ found 123[0874 "HRÐMS#[
Odour of M 30 "GC] 88)#] woody\ vetiver!like\
earthy\ patchouli!like[
Isolation of isovalencenol (41) from fraction V 3
(together with 40, see above)
Isovalencenol "30#
RI] 0664 "Sil 4#\ 1444 "wax#[ ðaŁD ¦82[1> "c 7\ C5D5\
GC] 73)#^ reference 5] ðaŁD ¦051[7> "c 1[7\ CHCl2#[ 0H!
NMR "CDCl2 ðC5D5Ł\ all coupling constants as given
for M 30#] d 9[70 ð9[80Ł "s\ 4!Me#\ 9[81 ð9[82Ł "d\ J  5[4
Hz\ 3!Me#\ 0[26 ð0[30Ł "dddd\ 2!Heq#\ 0[31 ð0[34Ł "dddd\
2!Hax#\ 0[36 ð0[43Ł "d\ br[\ 5!Hax#\ 0[49 ð0[41Ł "dqd\ 3!
Hax#\ 0[63 ð0[66Ł "dddd\ 7!Hax#\ 0[68 ð0[71Ł "dd\ 00!Me#\
0[82 ð0[85Ł "ddddd\ 1!Heq#\ 1[92 ð1[97Ł "dddd\ 1!Hax#\ 1[03
ð1[04Ł "ddd\ Hz\ 8!Heq#\ 1[12 ð1[20Ł "dddddd\ 8!Hax#\ 1[65
ð1[61Ł "dddd\ 7!Heq#\ 1[67 ð1[73Ł "dd\ 5!Heq#\ 3[02 ð3[92Ł
"dq# and 3[19 ð3[95Ł "d\ 00!CH1OH#\ 4[21 ð4[39Ł "ddd\ 0!
H#^ reference 5] d 9[71 "s#\ 9[82 "d\ J  4[4 Hz#\ 0[22
Copyright Þ 1999 John Wiley + Sons\ Ltd[
POLAR FRACTION OF HAITIAN VETIVER OIL 048
"OH#\ 0[64 "s#\ 3[01 "CH1OH#\ 4[2 "s\ br[#[ 02C!NMR]
see Table 3[
Odour of 30 "GC] 73)#] strong woody\ slightly cedar!
like[
Guaia-1(5),11-dien-3-yl methyl ether (M 11)
ðaŁD −29> "c 0[0\ CHCl2^ GC] 66)#[ 0H!NMR "with
COSY and NOED#] d 9[87 "d\ J  6 Hz\ 3!Me#\ 0[99
"d\ J  6 Hz\ 09!Me#\ 0[57 "mc\ 8!H1#\ 0[69 "mc\ 7!H1#\
0[60 "dd\ J  0[4\ 0[4 Hz\ 00!Me#\ 0[85 and 1[04 "1 d\
br[\ J  03 Hz\ 5!H1#\ 1[19 "mc\ 6!H#\ 1[11 "ddd\ br[\
J  05[4\ 2\ 1[4 Hz\ 1!H#\ 1[25 "q\ br[\ J  6 Hz\ 09!H#\
1[44 "q\ br[\ J  6 Hz\ 3!H#\ 1[62 "ddd\ br[\ J  05[4\ 6\
2 Hz\ 1?!H#\ 2[20 "s\ OMe#\ 2[31 "ddd\ J  6\ 2\ 1[4 Hz\
2!H#\ 3[51\ 3[56 "1 qd\ J  0[4\ 0[4 Hz\ 00!CH1#[ 02C!
NMR] see Table 4[ GCÐMS "HP#] m:z ")# 123 "M¦\
"099#\ 022 "21#\ 020 "34#\ 008 "26#\ 094 "43#\ 80 "44#\ 68
"21#\ 66 "20#\ 56 "10#\ 44 "12#[ C05H15O] calcd[ 123[0873\
found 123[0889 "HRÐMS#[
trans-Guai-11-en-10-ol (pogostol, 33)
RI "Sil 4#] 0543[ GC] 63)[ Reference 01] ðaŁD −07[8> "c
9[3\ CHCl2#[ 0H!NMR "with COSY and NOED#] d 9[78
"d\ J  5[4 Hz\ 3!Me#\ 0[08 "s\ 09!Me#\ 0[11 "mc\ 2!H#\
0[15 "ddd\ J  03\ 00\ 8 Hz\ 5!H#\ 0[39 "ddd\ J  03\ 0\
0 Hz\ 5?!H#\ 0[33 "ddddd\ J  04\ 09\ 8\ 7\ 2 Hz\ 7!H#\
0[44 "ddd\ br[\ J  02\ 6\ 5 Hz\ 1!H#\ 0[44 "mc\ 8!H#\
0[58 "dd\ J  0\ 0 Hz\ 00!Me#\ 0[61 "mc\ 2?!H#\ 0[63
"dddd\ J  02\ 7\ 6\ 3 Hz\ 1?!H#\ 0[73 "dddd\ J  04\ 09\
5\ 3 Hz\ 7?!H#\ 0[89 "ddd\ J  03\ 7\ 3 Hz\ 8?!H#\ 0[88
"dd\ br[\ J  00\ 8 Hz\ 4!H#\ 1[92 "q\ br[\ J  5[4 Hz\ 3!
H#\ 1[01 "ddd\ J  00\ 7\ 6 Hz\ 0!H#\ 1[15 "dddd\ J  00\
09\ 5\ 0 Hz\ 6!H#\ 3[47\ 3[55 "1 qd\ J  0\ 0 Hz\ 00!CH1#^
reference 01] d "CCl3# 9[78 "d\ 5#\ 0[01 "s#\ 0[56 "s#\ 3[42\
3[50 "1 br[\ s#[ 02C!NMR] see Table 4[ GCÐMS "HP#]
m:z ")# 111 "M¦\ 9[4#\ 194 "09#\ 193 "54#\ 078 "55#\ 051
"08#\ 050 "74#\ 037 "16#\ 036 "42#\ 024 "18#\ 023 "10#\ 022
"44#\ 010 "39#\ 008 "55#\ 098 "13#\ 097 "50#\ 096 "84#\ 095
"16#\ 094 "099#\ 84 "39#\ 83 "10#\ 82 "78#\ 80 "76#\ 70 "49#\
68 "58#\ 66 "37#\ 56 "26#\ 54 "08#\ 44 "21#\ 42 "13#[
Isolation of guaienol 44
Re!FC ð"a# SiO1\ PE:19) Et1O^ "b# Al1O2\ PE:19)
Et1OŁ of a medium polar fraction "9[08 g\ b[p[ 41>C:9[91
mbar# consisting mainly of khusimone F0 gave 0[ 9[02 g
of F\ 1[ 04 mg of 04!nor!funebran!6!one\0 2[ 5 mg of 33[
cis!Guai!5!en!09!ol "33#
RI "Sil 4#] 0464 "wax# 1999[ GC] 44)[ 0H!NMR "with
COSY and NOED#] d 9[884 "d\ J  6 Hz\ 3!Me#\ 0[99\
0[91 "1 d\ J  6 Hz\ 00!Me1#\ 0[01 "s\ 09!Me#\ 0[22 "mc\
2!H#\ 0[51 "mc\ 1!H#\ 0[52 "mc\ 2?!H#\ 0[64 "mc\ 8!H1#\
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
059 P[ WEYERSTAHL ET AL[

Table 5. 13C-NMR data (d, CDCl3) of the guaiene derivatives M 11, 33, 44 and (for comparison) a-guaiene C and
1,10-epoxyguai-11-ene D (for numbering, see Scheme 4)
C!No M 00a Cb 22a\c Dd 33a
0 s 025[5 s 039[5 d 44[3 s 64[6 d 40[7
1 t 31[1 t 25[2 t 15[0 t 18[3 t 13[4
2 d 75[8 t 20[2 t 20[0 t 26[0 t 21[0
3 d 41[3 d 35[5 d 27[8 d 26[4 d 27[9
4 s 026[6 s 027[6 d 34[7 d 37[7 d 32[1
5 t 22[2 t 22[3 t 17[4 t 29[1è d 011[1
6 d 35[9 d 35[6 d 35[0 d 49[4 s 038[0
7 t 29[8 d 20[1 t 17[4 t 29[5è t 14[8
8 t 22[5 t 23[9 t 25[0 t 18[0 t 27[5
09 d 22[5 t 22[8 s 63[8 s 52[2 s 62[6
00 s 041[0 s 041[0 s 041[3 s 040[2 d 25[6
3!Me q 06[7 q 08[7 q 05[0 q 04[0 q 04[7
09!Me q 07[5 q 07[5 q 18[6 q 19[2 q 18[7
00!Me q 19[3 q 19[3 q 08[8 q 19[7 q 10[0
00!CH1 t 097[9 t 097[9 t 096[6 t 097[5 00!Me q 10[3
OMe q 45[2

è Exchangeable values[
a
With 0H02C!correlation[
b
Values from reference 02[
c
In agreement with the data "without assignments there# given in reference 01[
d
Values from reference 03[

0[67 "mc\ 1?!H#\ 1[92 "ddd\ br[\ J  04\ 4\ 4 Hz\ 7!H#\
1[95 "ddq\ J  6\ 6\ 6 Hz\ 3!H#\ 1[08 "ddd\ J  8\ 8\ 7
Hz\ 0!H#\ 1[18 "qqdd\ J  6\ 6\ 0[4\ 0 Hz\ 00!H#\ 1[22
"mc\ 7?!H#\ 1[70 "dddd\ J  8\ 6\ 2\ 0 Hz\ 4!H#\ 4[33
"dddd\ J  2\ 0[4\ 0[4\ 0[4 Hz\ 5!H#[ 02C!NMR] see Table
4[ GCÐMS "HP#] m:z ")# 111 "M¦\ 2#\ 193 "08#\ 078
"13#\ 050 "099#\ 038 "05#\ 036 "07#\ 022 "12#\ 011 "34#\
010 "38#\ 008 "24#\ 098 "21#\ 096 "38#\ 094 "56#\ 84 "38#\
82 "49#\ 80 "49#\ 70 "49#\ 68 "43#\ 66 "25#\ 60 "20#\ 58
"28#\ 56 "25#\ 44 "35#[ C04H15O] calcd[ 111[0873\ found
111[0875 "HRÐMS#[
10-Methoxy-7,10-epoxysalvialane (M 8)
GC] 60)[ 0H!\ 02C!NMR] see Table 5[ GCÐMS "HP#]
m:z ")# 141 "M¦\ 0#\ 123 "0#\ 082 "1#\ 038 "2#\ 026 "2#\
018 "00#\ 013 "11#\ 012 "16#\ 098 "4#\ 096 "4#\ 094 "3#\ 82
"4#\ 80 "5#\ 71 "7#\ 70 "099#\ 79 "07#\ 68 "09#\ 66 "4#\ 58
"5#\ 56 "4#\ 44 "5#[ C05H17O1] calcd[ 141[1978\ found
141[1981 "HRÐMS#[
Preziza-7(15)-en-3a-yl methyl ether (M 14)
RI "wax#[ 0859[ ðaŁD ¦06> "c 9[8\ CHCl2\ GC] 71)#[
0
H!NMR "with COSY and NOED#] d 9[85 "d\ J  6[4
Hz\ 1!Me#\ 0[97\ 0[974 "1 s\ 5!Me1#\ 0[11 "ddd\ J  09[4\
1\ 1 Hz\ 00!Hendo#\ 0[15 "dddd\ J  03\ 02\ 3[4\ 0 Hz\
09!H#\ 0[40 "ddd\ J  02[4\ 5\ 0 Hz\ 4!H#\ 0[43 "ddd\
J  02[4\ 01\ 5[4 Hz\ 3!H#\ 0[43 "dd\ J  09[4\ 3[4 Hz\
00!Hexo#\ 0[48 "dddd\ J  02[4\ 8[4\ 3[4\ 1 Hz\ 8!H#\ 0[67
"qd\ J  6[4\ 1[4 Hz\ 1!H#\ 0[72 "dddd\ J  02[4\ 02\ 5[4\
4 Hz\ 8?!H#\ 1[95 "ddd\ J  01\ 6\ 5 Hz\ 3?!H#\ 1[01
"dddd\ J  03\ 8[4\ 4\ 1 Hz\ 09?!H#\ 1[79 "dd\ br[\ J  5[4\
3[4 Hz\ 7!H#\ 2[21 "s\ 2!OMe#\ 2[22 "ddd\ J  6\ 5[4\ 1[4
Hz\ 2!H#\ 3[55\ 3[60 "1 d\ J  0[4 Hz\ 6!CH1#[ 0H!NMR
"C5D5#] see Figure 0[ 02C!NMR] see Table 6[ GCÐMS
"HP#] m:z ")# 123 "M¦\ 04#\ 108 "8#\ 191 "04#\ 076 "13#\
048 "18#\ 034 "10#\ 022 "14#\ 021 "14#\ 020 "099#\ 008 "15#\
006 "12#\ 097 "36#\ 096 "13#\ 094 "24#\ 84 "07#\ 82 "24#\
80 "47#\ 70 "13#\ 68 "26#\ 66 "23#\ 60 "08#\ 56 "16#\ 44 "21#\
42 "15#[ C05H15O] calcd[ 123[0873\ found 123[0877 "HRÐ
MS#[

Hydrolysis of M 8
09!Hydroxy!6\09!epoxysalvialane "7#
RI "Sil 4#] 0531[ GC] 83)[ According to reference 04
stirring "0 d\ 19>C# of M 7 "39 mg# with Amberlystþ 04
"34 mg# in acetone "4 ml# gave 7 "29 mg\ 71)#[ 0H!\
02
C!NMR] see Table 5[ GCÐMS "HP#] m:z ")# 119
"M¦−H1O\ 3#\ 194 "1#\ 084 "1#\ 066 "6#\ 048 "2#\ 038 "5#\
026 "4#\ 013 "10#\ 012 "33#\ 098 "6#\ 096 "5#\ 82 "6#\ 80
"6#\ 70 "099#\ 79 "16#\ 68 "00#\ 66 "5#\ 58 "4#\ 56 "5#\ 44
"5#[
12-nor-Ziza-6(13)-en-2b
b -yl methyl ether (M 2)
GC] 42)\ mixture with 19) of M 2[ 0H!NMR "with
NOED#] d 0[95\ 0[09 "1 s\ 6!Me1#\ 0[49 "dd\ J  00[4\ 4
Hz\ 00!Hexo#\ 0[63 "dd\ J  03\ 8 Hz\ 2!H#\ 0[67 "dd\ br[\
J  4\ 4 Hz\ 7!H#\ 1[98 "ddd\ J  00[4\ 1\ 1 Hz\ 00!
Hendo#\ 1[62 "dddd\ br[\ J  8\ 7\ 1\ 1 Hz\ 4!H#\ 2[20 "s\
1!OMe#\ 2[27 "dd\ J  8\ 8 Hz\ 1!H#\ 3[59 "dd\ J  1\ 1
Hz# and 3[64 "dd\ J  1\ 0[4 Hz\ 5!CH1#[ 02C!NMR] see
Table 6[ GCÐMS "MAT#] m:z ")# 119 "M¦\ 0#\ 194
"1#\ 077 "63#\ 062 "56#\ 048 "08#\ 038 "10#\ 034 "099#\ 022

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
 POLAR FRACTION OF HAITIAN VETIVER OIL 050

Table 6. 1H- and 13C-NMR data (d, CDCl3) of the salvialane derivatives 8 and M 8 (for
numbering, see Scheme 5)
02 0
C:H C H J ðHzŁ
a b
7 M7 7 M7
0 s 37[5 38[9
1 t 22[4 29[7 0[23 0[26 dd br[ 01^ 7
1? 1[98 1[99 ddd br[ 01^01^7
2 t 18[1 18[1 0[41 0[36 ddd 02^8^7
2? 0[87 0[81 ddd 02^01^8^7
3 d 45[9 44[6 0[07 0[00 dddd 09^8^7^1
4 d 34[5 34[6 0[55 0[52 ddd 01^6^1
5 t 35[1 35[1 0[17 0[16 dd br[ 02^01
5? 0[41 0[40 dd 02^6
6 s 79[3 68[9
7 t 29[2 14[4 0[69 0[84 mc
8 t 23[1 22[8 0[54 0[50 d br[ 01
8? 1[28 0[61 ddd 7] 01^7^2^
M 7] 01^8^5
09 s 096[1 009[0
00 d 24[2 24[2 0[39 0[27 dqq 09^5[4^5[4
0!Me q 11[3 11[0 0[93 9[86 s
6!Me q 16[9 15[7 0[18 0[16 s
00!Me q 10[4 10[4 9[72 9[71 d 5[4
00!Me q 11[3 11[3 9[78 9[78 d 5[4
OR q 37[5 1[24 2[22 s
a
With 0H02C!correlation and NOED[
b
With HMBC[

"49#\ 021 "37#\ 020 "30#\ 008 "46#\ 006 "49#\ 094 "23#\ 82
"15#\ 80 "70#\ 68 "37#\ 66 "25#\ 56 "34#\ 44 "42#[ C04H13O]
calcd[ 119[0716\ found 119[0712 "HRÐMS#[
12-nor-Ziza-6(13)-en-2aa-yl methyl ether (M 3)
GC] 36)\ mixture with M 1[ 0H!NMR] d 0[96\ 0[964 "1
s\ 6!Me1#\ 0[26 "dddd\ J  02\ 8\ 3\ 3 Hz\ 2!H#\ 0[37 "dd\
J  00\ 3[4 Hz\ 00!Hexo#\ 0[57 "d\ br[\ J  00 Hz\ 00!
Hendo#\ 0[68 "dd\ br[\ J  4\ 4 Hz\ 7!H#\ 1[98 "dddd\
J  02\ 8\ 8\ 5 Hz\ 2?!H#\ 1[26 "dddd\ J  00\ 7\ 1\ 1 Hz\
4!H#\ 2[25 "s\ 1!OMe#\ 2[69 "dd\ J  8\ 7 Hz\ 1!H#\ 3[45
and 3[68 "1 dd\ J  1\ 0[4 Hz\ 5!CH1#[ 02C!NMR] see
Table 6[ GCÐMS "MAT#] m:z ")# 119 "M¦\ 2#\ 194
"09#\ 077 "06#\ 062 "03#\ 048 "8#\ 049 "20#\ 038 "82#\ 034
"32#\ 020 "10#\ 010 "20#\ 008 "67#\ 007 "27#\ 006 "51#\ 098
"23#\ 094 "25#\ 82 "25#\ 80 "099#\ 68 "44#\ 66 "39#\ 56 "36#\
44 "48#[
NaBH4 reduction of khusimone (F)
01!nor!Ziza!5"02#!en!1a!ol "2#\ RI] Sil 4 0592\ GC] 75)[
Obtained by NaBH3 reduction of khusimone "F#[0 0H!
NMR "with NOED#] d 0[93\ 0[94 "1 s\ 6!Me1#\ 0[22 "ddd\
J  02[4\ 8\ 3[4 Hz\ 2!H#\ 0[33 "mc\ 8!H\ 09!H#\ 0[46
"dd\ J  00\ 3[4 Hz\ 00!Hexo#\ 0[48 "dddd\ J  01\ 8\ 4[4\
3 Hz\ 3!H#\ 0[59 "mc\ 8?!H#\ 0[54 "dddd\ J  01\ 8[4\ 8\
3[4 Hz\ 3?!H#\ 0[55 "d\ br[\ J  00 Hz\ 00!Hendo#\ 0[60
"mc\ 09?!H#\ 0[62 "dd\ br[\ J  4\ 4 Hz\ 7!H#\ 1[98 "dddd\
J  02[4\ 8[4\ 8\ 4[4 Hz\ 2?!H#\ 3[97 "dd\ J  8\ 8 Hz\ 1!
H#\ 3[43 "dd\ J  0[4\ 0[4 Hz# and 3[66 "dd\ J  1\ 0[4
Hz\ 5!CH1#[ 02C!NMR] see Table 6[ GCÐMS "HP#] m:z
")# 195 "M¦\ 2#\ 080 "04#\ 077 "7#\ 066 "09#\ 062 "02#\
052 "02#\ 034 "15#\ 025 "37#\ 024 "099#\ 008 "45#\ 006 "34#\
098 "10#\ 097 "08#\ 094 "13#\ 84 "12#\ 82 "13#\ 80 "42#\ 70
"05#\ 68 "17#\ 66 "13#\ 56 "16#\ 44 "19#[ C03H11O] calcd[
195[0560\ found 195[0566 "HRÐMS#[
Odour of 2] "GC] 75)#] woody\ bitter\ patchouli!like[
Isolation of 12-nor-epoxyzizaene 45
Re!FC ð"a# SiO1^ "b# Al1O2\ PE:09) Et1OŁ of a non!
polar fraction "14 mg# gave as _rst fraction 4 mg of
kessane "E\ 0H! and 02C!NMR data in agreement with
those given in references 05Ð07#\ as second fraction 1
mg of 0\09!epoxyamorph!3!ene3 "GC] 54)#\ as third
fraction 2 mg of 34\ and as fourth fraction 3 mg of
09\00!epoxyeremophil!0!ene[1
01!nor!1\2!Epoxyziza!5"02#!ene "34#
RI] Sil 4 0449\ wax 1969\ GC] 59)\ with 19) of 0\09!
epoxy!amorph!3!ene[3 0H!NMR "CDCl2\ with COSY
and NOED#] d 0[95\ 0[96 "1 s\ 6!Me1#\ 0[97 "d\ br[\
J  03 Hz\ 09!Hendo#\ 0[01 "dddd\ J  03\ 8\ 5\ 1 Hz\ 09!
Hexo#\ 0[18 "dd\ J  02\ 5 Hz\ 8!Hexo#\ 0[36 "dddd\ J  02\
00\ 8\ 2 Hz\ 8!Hendo#\ 0[36 "ddd\ J  02[4\ 09\ 0 Hz\ 3!
H#\ 0[43 "dd\ J  00\ 3[4 Hz\ 00!Hexo#\ 0[74 "ddd\ J  00\
3[4\ 1 Hz\ 7!H#\ 0[86 "dd\ J  02[4\ 5[4 Hz\ 3?!H#\ 1[94
"ddd\ J  00\ 1\ 1 Hz\ 00!Hendo#\ 1[27 "ddddd\ J  09[4\
5[4\ 0[4\ 0[4\ 0[4 Hz\ 4!H#\ 2[19 "d\ J  2 Hz\ 1!H#\ 2[28
"d\ br[\ J  2 Hz\ 2!H#\ 3[49\ 3[62 "1 dd\ J  0[4\ 0[4 Hz\
5!CH1#[ 02C!NMR] see Table 6[ GCÐMS "HP#] m:z ")#

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
 051 P[ WEYERSTAHL ET AL[

Copyright Þ 1999 John Wiley + Sons\ Ltd[

Figure 1. 1H-NMR spectrum (400 MHz, C6D6) of preziza-7(15)-en-3a-yl methyl ether (M 14, GC: 82%) containing ziza-6(13)-en-3a-yl methyl ether (M 19 = Z)

Flavour Fra`r[ J[ 1999^ 04] 042Ð062

 POLAR FRACTION OF HAITIAN VETIVER OIL 052

Table 7. 13C-NMR data of the 12-nor-zizaene derivatives M 2, 3, M 3, 45, of the zizaene derivatives 19, M 19, 21,
M 21, 46, 47 and of prezizaen-3b-yl methyl ether M 14 (for numbering, see Scheme 6)
C!No[ M1 M2 2 34 M 08a 08b M 10 10b 35 36 M 03a
CDCl2 CDCl2 CDCl2 C5D5 CDCl2 CDCl2 CDCl2 CDCl2 C5D5 C5D5 C5D5

0 s 45[4 43[0 43[4 41[2 42[3 42[6 43[2 43[3 43[1 42[5 41[5
1 d 78[4 73[5 64[8 59[1 35[5 49[4 33[3 35[9 39[5 33[6 36[1
2 d 12[6 19[8 19[2 43[5 78[8 70[0 71[8 62[7 68[9 62[6 78[5
3 t 18[9 11[3 11[1 17[6 21[8 22[5 29[4 21[6 24[3 25[8 20[2
4 d 35[5 36[2 36[9 32[2 34[8 35[7 33[4 34[3 38[2 49[3 42[0
5 s 046[0 045[3 045[3 045[1 045[9 045[9 045[5 045[3 045[2 045[1 26[4
6 s 39[3 39[2 39[3 39[3 39[0 39[1 39[3 39[4 30[5 39[6 051[0
7 d 38[9 37[5 37[5 40[5 37[6 37[8 37[5 37[8 37[3 37[6 36[8
8 t 14[7 14[4 14[3 15[2 15[9 15[0 15[0 14[8 10[7 11[8 29[1
09 t 18[0 17[3 20[4 16[1 22[0 25[1 21[0 23[7 15[1 15[6 22[2
00 t 24[3 27[2 26[0 26[9 25[1 25[2 25[0 25[3 27[4 27[8 30[2
1!Me q Ð Ð Ð Ð 06[8 06[9 00[9 00[9 01[0 7[9 1!Me 06[8
5!CH1 q 094[1 094[3 094[3 094[6 094[1 094[2 093[7 093[8 094[3 094[4 5!Me 16[0
6!Me q 15[1 15[0 14[0 15[7 15[9 15[0 15[2 15[1 15[3 15[2 5!Me 21[0
6!Me q 17[5 17[6 17[5 18[9 17[2 17[3 17[5 17[5 17[5 17[6 6!CH1 095[2
OMe q 45[7 46[7 Ð Ð 45[8 Ð 46[3 Ð Ð Ð 45[6
 Exchangeable values[
a
With 0H02C!correlation[
b
Values from reference 08\ without multiplicities and assignments there\ tentative assignments by us[

193 "M¦\ 08#\ 078 "41#\ 064 "05#\ 060 "05#\ 050 "099#\
036 "26#\ 032 "20#\ 022 "26#\ 020 "18#\ 010 "20#\ 008 "39#\
006 "18#\ 096 "18#\ 094 "41#\ 80 "54#\ 68 "39#\ 66 "39#\ 56
"15#\ 44 "13#[ C03H19O] calcd[ 193[0403\ found 193[0419
"HRÐMS#[
Ziza!5"02#!en!2a!yl methyl ether "M 08#
RI "wax# 0871[ GC] 65)\ with 08) of b!funebren!03!
yl methyl ether "RI] wax 0834# M 02[0 0H!NMR "with
COSY and NOED#] d 0[92 "d\ J  6[4 Hz\ 1!Me#\ 0[93\
0[96 "1 s\ 6!Me1#\ 0[23 "dd\ J  00\ 4 Hz\ 00!Hexo#\ 0[28
"ddd\ J  00\ 3\ 1 Hz\ 8!H#\ 0[34 "ddd\ J  00\ 5\ 4 Hz\
8?!H#\ 0[41 "ddd\ J  01[4\ 01[4\ 6 Hz\ 3!H#\ 0[47 "mc\
09!H#\ 0[63 "dd\ br[\ J  5\ 4 Hz\ 7!H#\ 0[68 "qd\ J  6[4\
1[4 Hz\ 1!H#\ 0[70 "ddd\ J  00\ 1\ 1 Hz\ 00!Hendo#\ 1[98
"ddd\ J  01[4\ 6\ 5[4 Hz\ 3?!H#\ 1[40 "ddddd\ J  01[4\
5[4\ 1\ 1\ 0[4 Hz\ 4!H#\ 2[29 "s\ 2!OMe#\ 2[39 "ddd\ J  6\
6\ 1[4 Hz\ 2!H#\ 3[47 "dd\ J  1\ 0[4 Hz# and 3[62 "dd\
J  1\ 1 Hz\ 5!CH1#[ Values of ziza!5"02#!en!2a!ol "08#
from reference 08 for comparison] d 0[92 "d\ J  5[3
Hz#\ 0[94\ 0[96 "1 s#\ 1[00 "d#\ 1[42 "m#\ 2[75 "dt\ J  2[1\
6[1 Hz\ 2!H#\ 3[46\ 3[63 "1 t\ J  0[5 Hz#[ 02C!NMR] see
Table 6[ GCÐMS "MAT#] m:z ")# 123 "M¦\ 4#\ 108
"5#\ 191 "08#\ 076 "6#\ 053 "44#\ 048 "07#\ 034 "02#\ 022
"099#\ 021 "34#\ 020 "88#\ 008 "14#\ 006 "14#\ 098 "15#\
097 "28#\ 096 "18#\ 094 "24#\ 84 "12#\ 82 "20#\ 80 "44#\ 68
"26#\ 66 "10#\ 56 "22#\ 44 "41#\ 42 "29#[ C05H15O] calcd[
123[0873\ found 123[0870 "HRÐMS#[
Ziza!5"02#!en!2b!yl methyl ether "M 10#
GC] 14)[ 0H!NMR] d 9[83 "d\ J  6 Hz\ 1!Me#\ 0[94\
0[97 "1 s\ 6!Me1#\ 0[25 "dd\ J  00\ 4 Hz\ 00!Hexo#\ 0[59
"mc\ 3!H#\ 0[67 "dd\ br[\ J  4\ 4 Hz\ 7!H#\ 0[81 "d\ br[\
J  00 Hz\ 00!Hendo#\ 1[92 "mc\ 1!H\ 3?!H#\ 1[79 "ddddd\
J  09\ 8\ 0[4\ 0[4\ 0[4 Hz\ 4!H#\ 2[18 "s\ 2!OMe#\ 2[70
"ddd\ J  8\ 5[4\ 3[4 Hz\ 2!H#\ 3[59 and 3[64 "1 dd\
J  0[4\ 0[4 Hz\ 5!CH1#[ Values of ziza!5"02#!en!2b!ol
"10# from reference 08 for comparison] d 9[87 "d\ J  7
Hz#\ 0[95\ 0[09 "1 s#\ 1[74\ 3[24 "dt\ J  2[4\ 6 Hz\ 2!H#\
3[48\ 3[65 "1 t\ J  0[4 Hz#[ 02C!NMR] see Table 6[ GCÐ
MS "MAT#] m:z ")# 123 "M¦\ 1#\ 191 "48#\ 076 "099#\
062 "15#\ 048 "80#\ 035 "35#\ 034 "23#\ 022 "51#\ 021 "25#\
020 "56#\ 008 "08#\ 006 "10#\ 096 "17#\ 094 "42#\ 84 "08#\
82 "39#\ 80 "68#\ 68 "46#\ 66 "30#\ 56 "59#\ 54 "20#\ 44 "80#\
42 "48#[
NaBH4 reduction of 2-epi-zizaen-3-one
NaBH3 reduction of 1!epi!ziza!5"02#!en!2!one0 gave a
mixture "0 ] 0# of 35 and 36\ which was separated by FC\
36 eluted as _rst fraction[
1!epi!Ziza!5"02#!en!2a!ol "36#
RI "Sil 4#] 0552\ wax 1274[ ðaŁD ¦1[3> "c 9[4\ CHCl2\
GC] 63)#[ 0H!NMR] d 9[82 "d\ J  6[4 Hz\ 1!Me#\ 0[96\
0[98 "1 s\ 6!Me1#\ 0[37 "dd\ J  00\ 4 Hz\ 00!Hexo#\ 0[50
"d\ br[\ J  00 Hz\ 00!Hendo#\ 0[61 "dd\ br[\ J  4\ 4 Hz\
7!H#\ 0[89 "qd\ J  6\ 6 Hz\ 1!H#\ 1[16 "ddd\ J  02\ 6\
6 Hz\ 3!H#\ 1[20 "ddddd\ J  6\ 6\ 0[4\ 0[4\ 0[4 Hz\ 4!
H#\ 3[12 "ddd\ J  6\ 6\ 3 Hz\ 2!H#\ 3[46 and 3[66 "1 dd\
J  0[4\ 0[4 Hz\ 5!CH1#[ 02C!NMR] see Table 6[ GCÐ
MS "HP#] m:z ")# 119 "M¦\ 5#\ 194 "00#\ 191 "10#\ 076
"04#\ 048 "21#\ 049 "099#\ 022 "34#\ 020 "68#\ 008 "13#\
006 "13#\ 096 "23#\ 094 "21#\ 82 "24#\ 80 "37#\ 70 "15#\ 68
"24#\ 66 "16#\ 56 "15#\ 44 "12#[ C04H13O] calcd[ 119[0716\
found 119[0729 "HRÐMS#[
Odour of 36 "GC] 63)#] strong woody\ ambra!\ veti!
ver!\ grapefruit!like[

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
053 P[ WEYERSTAHL ET AL[
1!epi!Ziza!5"02#!en!2b!ol "35#
RI "Sil 4#] 0544\ wax 1319[ ðaŁD ¦26[1> "c 9[4\ CHCl2\
GC] 69)#[ 0H!NMR "with NOED#] d 9[74 "mc\ 09!H#\
9[86 "d\ J  6[4 Hz\ 1!Me#\ 0[95\ 0[09 "1 s\ 6!Me1#\ 0[09
"mc\ 09?!H#\ 0[31 "mc\ 8!H#\ 0[36 "dd\ J  00\ 4 Hz\ 00!
Hexo#\ 0[45 "ddd\ J  03\ 7\ 1[4 Hz\ 3!H#\ 0[60 "ddd\ br[\
J  00\ 1\ 1 Hz\ 00!Hendo#\ 0[63 "dd\ br[\ J  5\ 4 Hz\ 7!
H#\ 0[74 "qd\ J  6\ 6 Hz\ 1!H#\ 1[94 "ddd\ J  03\ 00\
8[4 Hz\ 3?!H#\ 1[60 "ddddd\ J  00\ 7\ 0[4\ 0[4\ 0[4 Hz\
4!H#\ 2[67 "ddd\ J  8[4\ 6\ 1[4 Hz\ 2!H#\ 3[43 and 3[64
"dd\ J  0[4\ 0[4 Hz\ 5!CH1#[ 02C!NMR] see Table 6[
GCÐMS "HP#] m:z ")# 119 "M¦\ 1#\ 194 "6#^ 191 "57#\
076 "70#\ 062 "15#\ 048 "70#\ 049 "44#\ 034 "20#\ 022 "37#\
020 "099#\ 008 "23#\ 006 "21#\ 096 "28#\ 094 "33#\ 82 "49#\
80 "57#\ 70 "28#\ 68 "45#\ 66 "30#\ 56 "33#\ 44 "42#[
Ziza!5"02#!en!01!yl methyl ether "khusimyl methyl
ether\ M 29#
0
H\ 02C!NMR and MS data] see reference 0[
Odour of M 29 "GC] 77)#] strong\ typical vetiver!
and vetiveryl acetate!like\ woody\ grapefruit!like[ Odour
of khusimol 29 "GC] 79)#] woody\ grapefruit!\ vetiver!
like[
Reaction of khusimyl methyl ether M 30 with BBr3
BBr2 "9[97 ml# was added via syringe at −67>C to a
solution of M 29 "9[19 g# in CH1Cl1 "19 ml#[ The stirred
mixture was warmed slowly to −29>C^ after 5 h\ a satd[
NaHCO2 solution was added\ then the mixture was
allowed to warm to room temperature[ Usual work!up
yielded a 0 ] 0 mixture "9[06 g# of M 37 and M 29[ FC
enriched M 37 up to 79)[
Ziza!4!en!01!yl methyl ether "isokhusimyl methyl ether\
M 37#
RI "Sil 4# 0516[ GC] 79)[ ðaŁD ¦25[7> "c 9[2\ CHCl2#[
0
H!NMR] d 9[86\ 0[99 "1 s\ 6!Me1#\ 0[28 "dd\ J  00\ 4
Hz\ 00!H#\ 0[34 "dd\ J  0[4\ 0[4 Hz\ 5!Me#\ 0[4Ð0[7 "m\
7 H#\ 0[59 "dd\ br[\ J  00\ 0[4 Hz\ 00?!H#\ 0[77 "dd\
J  6\ 4 Hz\ 7!H#\ 1[98 "dddd\ J  8\ 5\ 5\ 2 Hz\ 1!H#\
1[07 "dddd\ br[\ J  8\ 5\ 0[4\ 0 Hz\ 3?!H#\ 2[98 "dd\
J  8\ 8 Hz# and 2[20 "dd\ J  8\ 5 Hz\ 01!H1#\ 2[22 "s\
OMe#[ 02C!NMR] d 02[2 "q\ 5!Me#\ 14[1\ 17[3 "1 q\ 6!
Me1#\ 13[0\ 15[5\ 15[6 "2 t\ C!2\ C!3\ C!8#\ 22[8 "t\ C!09#\
28[2 "t\ C!00#\ 39[2 "s\ C!6#\ 35[9 "d\ C!1#\ 37[9 "d\ C!7#\
40[7 "s\ C!0#\ 47[5 "q\ OMe#\ 63[0 "t\ C!01#\ 016[8\ 030[3
"1 s\ C!4\ C!5#[ GCÐMS "HP#] m:z ")# 123 "M¦\ 02#\
108 "05#\ 089 "04#\ 078 "099#\ 059 "09#\ 048 "57#\ 034 "00#\
022 "39#\ 020 "05#\ 018 "7#\ 008 "05#\ 006 "5#\ 004 "5#\ 094
"04#\ 80 "05#\ 68 "4#\ 66 "5#[ C05H15O] calcd[ 123[0873\
found 123[0878 "HRÐMS#[
Odour of M 37 "GC] 79)#] warm\ woody\ khus!
imone!\ ambra!like[
Copyright Þ 1999 John Wiley + Sons\ Ltd[
Reaction of M 30 with TMSI
Via syringe\ TMSI "9[09 ml# was added with stirring at
−49>C to a solution of M 29 "9[02 g# in CH1Cl1 "09 ml#[
Usual work!up after 19 min yielded a product "9[09 g#
which consisted of a 0 ] 0 mixture of M 37 and khusimyl
iodide "0H!NMR#[
Khusian-2-yl methyl ether (helifolan-2-yl methyl
ether, M 10)
RI "wax#] 0759[ GC] 74)[ 0H! and 02C!NMR] see Table
7[ GCÐMS "HP#] m:z ")# 125 "M¦\ 17#\ 110 "7#\ 193
"52#\ 078 "26#\ 067 "30#\ 066 "099#\ 065 "41#\ 050 "64#\
036 "14#\ 024 "17#\ 023 "29#\ 022 "26#\ 011 "35#\ 010 "42#\
008 "74#\ 096 "44#\ 094 "22#\ 87 "30#\ 85 "22#\ 82 "28#\ 80
"49#\ 74 "20#\ 72 "29#\ 70 "29#\ 68 "39#\ 56 "14#\ 44 "45#[
C05H17O] calcd[ 125[1039\ found 125[1026 "HRÐMS#[
Odour of M 09 "GC] 74)#] strong\ woody "fruity#[
Isolation of khusian-2-ol (helifolan-2-ol, 10)
FC of a medium polar fraction "1[9 g\ b[p[ 62>C:9[91
mbar# gave 9[69 g of 09 "GC] 71)#[
Khusian!1!ol "helifolan!1!ol\ 09#
RI] Sil 4 0563\ wax 1239[ m[p[ 79>C\ reference 19] 70>C[
ðaŁD −72> "c 09\ CHCCl2\ GC] 74)#^ reference 19] −55>
"c 0[3#[ 0H! and 02C!NMR] see Table 7[ GCÐMS "HP#]
m:z ")# 111 "M¦\ 21#\ 193 "05#\ 078 "16#\ 066 "099#\ 050
"24#\ 040 "18#\ 024 "19#\ 022 "34#\ 012 "19#\ 011 "26#\ 010
"23#\ 008 "50#\ 098 "16#\ 096 "39#\ 094 "21#\ 85 "19#\ 84
"20#\ 82 "23#\ 80 "39#\ 70 "11#\ 68 "11#\ 44 "07#[
Odour of 09 "GC] 71)#] pleasant\ woody\ fruity\ ten!
acious[
NaBH4 reduction of khusian-2-one
1!epi!Khusian!1!ol "38# was obtained by NaBH3
reduction of khusione[0 RI "Sil 4#] 0551\ wax 1207[ GC]
69)[ 0H! and 02C!NMR] see Table 7[ GCÐMS "MAT#]
m:z ")# 111 "M¦\ 6#\ 193 "06#\ 078 "13#\ 066 "08#\ 050
"23#\ 022 "44#\ 010 "24#\ 008 "099#\ 098 "39#\ 097 "29#\
096 "34#\ 094 "49#\ 85 "29#\ 84 "41#\ 82 "48#\ 80 "55#\ 72
"29#\ 71 "24#\ 70 "49#\ 68 "32#\ 58 "34#\ 56 "30#\ 44 "58#[
Helifol-1-en-14-yl methyl ether (khusien-14-yl
methyl ether, M 12)
RI "wax#] 0839[ GC] 34)\ mixture with 02) of M 6
and 14) of M 29[ 0H!\ 02C!NMR] see Table 8[ GCÐ
MS "HP#] m:z ")# 123 "M¦\ 06#\ 108 "1#\ 191 "09#\ 078
"099#\ 048 "34#\ 036 "02#\ 034 "02#\ 022 "22#\ 021 "14#\
020 "22#\ 019 "06#\ 008 "33#\ 007 "14#\ 006 "06#\ 096 "19#\
094 "61#\ 80 "39#\ 66 "04#\ 58 "89#[
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
 POLAR FRACTION OF HAITIAN VETIVER OIL 054

Table 8. 1H- and 13C-NMR data (d, CDCl3) of khusiol 10, M 10 and 2-epi-khusiol 49, (for numbering, see Scheme 7)
02 0
C:H C H J ðHzŁ 38d J ðHzŁ
a\b aÐc
09 M 09 38 09 M 09

0b t 39[6 27[9 30[5 1[97 0[87 ddd 01[4^8[4^2 0[24 ddd 02[4^1^1
0a 0[96 0[03 dd 01[4^4[4 0[76 dd 02[4^09
1 d 60[9 79[0 68[5 2[86 2[27 ddd 8[4^4[4^1 2[58 dd 09^1
2 s 28[6 28[6 27[6
3endo t 13[1 14[0 29[9 0[11 0[11 dddd 02^00^1^1
3exo 0[48 0[48 ddd 02^00^7
4endo t 20[9 29[8 29[7 0[34 0[35 mc
4exo 0[02 0[01 dddd 01^00^1^1
5 s 30[2 30[0 30[7
6 d 39[9 39[1 39[9 0[36 0[36 qdd 6^6^6
7b t 24[9 24[9 23[7 0[83 0[84 dddd 01[4^6^6^1 0[85 dddd 01[4^7^7^1
7a 9[86 9[86 dddd 01[4^00^6^6
8b t 13[1 13[2 13[1 0[36 0[34 dddd 01^6^6^6
8a 0[26 dddd 01^00^00^6
09 d 42[0 42[1 42[9 0[14 0[11 ddd 00^6^1
00 s 23[4 23[3 24[5
2!Me q 05[0 05[4 07[9 9[64 9[64 s 9[72
6!Me q 06[5 06[6 06[4 9[70 9[704 d 6 9[71 d 6
00!Me q 10[9 19[6 12[9 9[78 9[764 s 9[78
00!Me q 15[2 15[4 18[1 9[75 9[76 s 0[00
1!OMe q 45[6 2[22 s
a
With 0H02C correlation and NOED[
b
The enantiomer called allo!cedrol was isolated from Biota orientalis and Juniperus ri`ida[10 0H! and 02C!NMR data are in agreement with the values given
for allo!cedrol in reference 11[
c
Reference 19] "CCl3# d 9[62\ 9[75\ 9[78 "2 s#\ 9[70 "d#\ 2[75 "{oct|\ J  8^ 5^ 1 Hz#[
d
Reference 19] "CCl3# d 9[72\ 9[75\ 0[09 "2 s#\ 9[79 "d#\ 2[50 "dd\ J  1[4^ 8 Hz#[

Table 9. 1H- and 13C-NMR data (d, CDCl3) of helifolen-14-yl methyl ether M 12 and helifolene D
50 for comparison (for numbering, see Scheme 7)
02 0
C:H C H J ðHzŁ
a b b a
M 01 49 49 M 01
0 d 023[5 d 023[5 5[18 5[25 d 7[4
1 d 028[2 d 028[0 4[74 4[73 d 7[4
2 s 30[4 s 30[4
3 t 21[3 t 21[4 9[77 mc
3? 0[51 dd br[ 09^8
4 t 17[9 t 16[4 9[82 mc
4? 0[41 mc
5 s 36[8 s 37[7
6 d 31[8 d 26[0 0[61 0[76 dd br[ 7^5
7 t 17[7 t 22[8 0[49 mc
7? 0[85 ddd br[ 02^8^7
8 t 12[4 t 12[2 0[33 mc
8? 0[43 mc
09 d 45[2 d 43[6 0[12 0[06 ddd 01[4^6^0[4
00 s 23[9 s 23[0
2!Me q 08[4 q 08[3 0[93 0[91 s
00!Meendo q 19[6 q 19[6 9[74 9[73 s
00!Meexo q 29[7 q 29[8 9[65 9[64 s
6!CH1 t 65[4 q 19[9 9[86c 2[08 dd 8^5
2[34 dd 8^7
OMe q 47[5 Ð Ð 2[23 s
a 0 02
With H C!correlation and NOED[
b
Data from reference 12[
c
Helifolene D 49] 6!Me\ d\ J  6 Hz[

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
055 P[ WEYERSTAHL ET AL[

Table 10. 13C-NMR data (d, CDCl3) of the spirovetivadiene derivatives M 39, M 42, M 43, 51, 53 and (for
comparison) b-vetivone 52 and spirovetivadien-15-al G (for numbering, see Scheme 8)
C No[ M 31 40a Gb 41c M 28 M 32 42
0 t 15[7 15[6 15[2 t 31[8 t 23[9 d 86[7 t 32[4
1 t 11[3 11[3 13[5 s 088[0 s 036[3 s 048[0 s 105[0
2 d 011[9 012[9 041[3 d 015[9 d 87[5 s 39[4 s 38[8
3 s 031[9 025[8 035[5 s 056[1 s 045[9 s 046[3 s 044[8
4 s 37[5 37[9 35[8 s 40[9 s 49[9 s 41[9 s 41[2
5 t 27[9 39[8 25[4è t 27[9 t 39[7 t 39[3 t 30[1
6 s 027[2 057[0 024[6 s 022[7 s 024[4 s 023[6 s 022[5
7 t 17[8 17[4 18[4 t 18[3 t 17[2 t 17[0 t 17[2
8 t 26[7 26[4 26[2è t 26[6 t 26[4 t 27[9 t 25[7
09 d 25[0 25[0 25[0 d 28[9 d 28[3 d 27[7 d 27[1
00 s 010[8 017[3 019[3 s 011[5 s 019[5 s 019[6 s 010[3
3!Me q 19[2 19[1 084[0d 3!Me t 10[6 3!CH1 t 096[0 t 098[0 t 009[8
09!Me q 04[6 04[6 04[3 09!Me q 05[5 09!Me q 06[9 q 08[3 q 07[4
00!Me q 05[7 00[4 19[8 00!Me q 10[9 00!Me q 19[8 q 19[6 g 19[7
00!Re t 62[8 d 080[5 q 10[9 00!Me q 10[0 00!Me q 10[9 q 19[8 q 19[8
01!OMe q 46[2 Ð Ð Ð 1!OMe q 43[3 q 43[2 q Ð
2!Me Ð q 18[7 q 29[7
2!Me q 18[1 q 16[3
è
Exchangeable values[
a
With 0H02C!correlation[
b
Some assignments of the C1C singlets given in reference 13 have been changed[
c
In agreement with reference 14[
d
3!CHO] d[
e
M 31] R  CH1OMe^ 40] R  CHO\ d^ G] R  Me\ q[

Spirovetiva-3,7(11)-dien-12-yl methyl ether (M 42) MnO2 oxidation of the polar fraction V 3

GC] 44)\ mixture with 24) of M 30[ 0H!NMR] d 9[76
"d\ J  6 Hz\ 09!Me#\ 0[52 "dd\ J  0[4\ 0[4 Hz\ 3!Me#\
0[58 "dd\ J  0[4\ 0[4 Hz\ 00!Me#\ 0[75 "dq\ br[\ J  02\
6 Hz\ 09!H#\ 0[81\ 0[87 "1 mc\ 1!H1#\ 1[13\ 1[18 "1 d\ br[\
J  05 Hz\ 5!H1#\ 1[26 "dd\ br[\ J  06\ 7 Hz# and 1[34
"dd\ br[\ J  06\ 6 Hz\ 7!H1#\ 2[16 "s\ 01!OMe#\ 2[76 "s\
br[\ 01!H1#\ 4[23 "mc\ 2!H#[ 02C!NMR] see Table 09[
GCÐMS "HP#] m:z ")# 123 "M¦\ 9[94#\ 191 "36#\ 076
"07#\ 062 "7#\ 059 "099#\ 034 "81#\ 020 "15#\ 008 "12#\ 094
"20#\ 82 "18#\ 80 "39#\ 68 "08#\ 66 "13#\ 54 "00#\ 44 "00#\
42 "00#[
Isolation of spirovetivadienol 42
Compound 31 was obtained after MnO1 oxidation of
fraction V 2 "see below# and NaBH3 reduction of the
product[
MnO1 oxidation of the polar fraction V 2 "1[4 g# gave a
mixture of aldehydes and ketones "9[6 g#[ Repeated FC
"2×\ SiO1\ PE:09) Et1O# gave as _rst fraction 09 mg
of 40 "GC] 55)# and as second fraction 19 mg of a
mixture of khusimone F "39)# and 40 "39)#[
Spirovetiva!2\6"00#!dien!01!al "40#
RI] Sil 4 0794[ GC] 55)[ 0H!NMR "with NOE#] d 9[77
"d\ J  6 Hz\ 09!Me#\ 0[52 "ddd\ J  0[4\ 0[4\ 0[4 Hz\ 3!
Me#\ 0[64 "dddd\ J  0[4\ 0[4\ 0\ 0 Hz\ 00!Me#\ 0[84\
1[94 "1 mc\ 1!H1#\ 1[40\ 1[43 "1 d\ br[\ J  07 Hz\ 5!H1#\
1[84 and 1[88 "1 dd\ br[\ J  08\ 7 Hz\ 7!H1#\ 4[30 "mc\
2!H#\ 8[84 "s\ CHO#[ 02C!NMR] see Table 09[ GCÐMS
"HP#] m:z ")# 107 "M¦\ 7#\ 193 "1#\ 078 "7#\ 066 "02#\
065 "86#\ 037 "02#\ 036 "099#\ 008 "10#\ 094 "12#\ 82 "8#\
80 "19#\ 68 "8#\ 66 "02#\ 44 "09#[ C04H11O] calcd[ 107[0560\
found 107[0568 "HRÐMS#[

Spirovetiva!2\6"00#!dien!01!ol "31#
RI] Sil 4 0669[ GC] 39)\ mixture with 39) of 01!nor!
ziza!5"02#!en!1a!ol "2#[ 0H!NMR] d 9[75 "d\ J  6 Hz\
09!Me#\ 0[51 "ddd\ J  0[4\ 0[4\ 0[4 Hz\ 3!Me#\ 0[63
"dddd\ J  0[4\ 0[4\ 0\ 0 Hz\ 00!Me#\ 0[74 "dq\ br[\
J  02\ 6 Hz\ 09!H#\ 0[89\ 1[99 "1 mc\ 1!H1#\ 1[11\ 1[16
"1 d\ br[\ J  06 Hz\ 5!H1#\ 1[28 and 1[30 "1 d\ br[\
J  07 Hz\ 7!H1#\ 3[98 "s\ br[\ 01!H1#\ 4[22 "mc\ 2!H#[
GCÐMS "HP#] m:z ")# 119 "M¦\ 1#\ 191 "26#\ 076 "02#\
062 "09#\ 059 "099#\ 034 "89#\ 020 "12#\ 094 "16#\ 82 "16#\
80 "28#\ 68 "06#\ 66 "10#\ 56 "5#\ 54 "8#\ 44 "6#\ 42 "7#[
Artefacts
2-Methoxyspirovetiva-2,4(15),7(11)-triene (M 39)
GC] 81)[ 0H!NMR "CDCl2\ ðC5D5Ł\ with NOED#] d
9[77 ð0[90Ł "d\ J  6 Hz\ 09!Me#\ 0[36 ð0[31Ł "ddd\
J  01\ 01\ 8 Hz\ 8!H#\ 0[50\ 0[56 ð0[57\ 0[62Ł "1 d\ br[\
J  0 Hz\ 00!Me1#\ 0[61 ð0[47Ł "qdd\ J  6\ 5\ 1 Hz\ 09!
H#\ 0[65 ð0[82Ł "dddd\ J  01\ 7\ 0\ 0 Hz\ 8?!H#\ 0[70
ð0[87Ł "dd\ J  06\ 1 Hz\ 0!H#\ 0[86 ð1[99Ł "d\ br[\ J  05
Hz\ 5?!H#\ 1[13 ð1[20Ł "dddq\ J  05\ 7\ 0\ 0 Hz\ 7!H#\

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062

1[16 ð1[41Ł "ddd\ br[\ J  05\ 01\ 8 Hz\ 7?!H#\ 1[48 ð1[69Ł
"ddd\ J  06\ 5\ 1 Hz\ 0?!H#\ 1[48 ð1[67Ł "d\ br[\ J  05
Hz\ 5?!H#\ 2[59 ð2[17Ł "s\ 1!OMe#\ 3[41\ 3[61 ð3[77\ 3[85Ł
"1 d\ J  0 Hz\ 3!CH1#\ 4[13 ð4[20Ł "d\ J  1 Hz\ 2!H#[
02
C!NMR] see Table 09[ GCÐMS "HP#] m:z ")# 121
"M¦\ 87#\ 106 "87#\ 193 "08#\ 078 "21#\ 064 "07#\ 050 "15#\
040 "28#\ 038 "60#\ 027 "18#\ 026 "15#\ 024 "49#\ 023 "099#\
012 "31#\ 008 "10#\ 004 "07#\ 094 "12#\ 84 "16#\ 80 "45#\
68 "13#\ 66 "24#\ 56 "18#\ 54 "07#\ 44 "13#\ 42 "08#[
C05H13O] calcd[ 121[0716\ found 121[0714 "HRÐMS#[
Odour of M 28 "GC] 81)#] bitter\ rhubarb!\ tagetes!\
vetiver!like[
2-Methoxy-3,3-dimethylspirovetiva-1,4(15),7(11)-
triene (M 43)
GC] 89)[ ðaŁD ¦70> "c 9[2\ CHCl2#[ 0H!NMR "CDCl2\
ðC5D5Ł#] d 9[71 ð0[92Ł "d\ J  6 Hz\ 09!Me#\ 9[76 ð9[87Ł
"ddd\ J  01\ 8\ 4 Hz\ 8!H#\ 0[12\ 0[17 ð0[40\ 0[42Ł "1 s\
2!Me1#\ 0[44 ð0[57Ł "ddd\ br[\ J  01\ 8\ 8 Hz\ 7!H#\ 0[59\
0[57 ð0[57\ 0[64Ł "1 s\ br[\ 00!Me1#\ 0[81 ð1[01Ł "dddd\
J  01\ 8\ 3\ 0[4 Hz\ 8?!H#\ 1[91 ð1[02Ł "d\ br[\ J  05
Hz\ 5!H#\ 1[92 ð1[97Ł "qd\ J  6\ 6 Hz\ 09!H#\ 1[07 ð1[20Ł
"d\ br[\ J  01 Hz\ 7?!H#\ 1[35 ð1[53Ł "d\ br[\ J  05 Hz\
5?!H#\ 2[40 ð2[17Ł "s\ 1!OMe#\ 3[61 ð3[57Ł "d\ J  6 Hz\
0!H#\ 3[72\ 4[09 ð4[98\ 4[14Ł "1 s\ 3!CH1#[ 02C!NMR] see
Table 09[ GCÐMS "HP#] m:z ")# 159 "M¦\ 45#\ 134
"26#\ 106 "16#\ 102 "20#\ 078 "13#\ 074 "12#\ 066 "44#\ 062
"08#\ 038 "10#\ 034 "10#\ 026 "16#\ 023 "24#\ 015 "16#\ 008
"15#\ 004 "10#\ 000 "23#\ 094 "20#\ 82 "08#\ 80 "45#\ 74
"099#\ 68 "23#\ 66 "21#\ 58 "12#\ 56 "13#\ 44 "21#\ 42 "13#[
C07H17O] calcd[ 159[1039\ found 159[1025 "HRÐMS#[
Hydrolysis of M 43
2\2!Dimethylspirovetiva!3"04#\6"00#!dien!1!one "42#
RI] Sil 4 0671\ GC] 72)[ According to reference 04
stirring "0 d\ 19>C# of M 32 "34 mg# with Amberlystþ
04 "49 mg# in acetone "4 ml# gave 42 "24 mg\ 71)#[ IR
"CCl3#] 0609 "CO#\ 0569\ 0529 "C1C# cm −0[ 0H!NMR
"CDCl2\ ðC5D5Ł#] d 9[76 ð9[87Ł "dd\ br[\ J  02\ 5[4 Hz\
8!H#\ 9[82 ð9[68Ł "d\ J  6 Hz\ 09!Me#\ 0[29\ 0[20 ð0[21\
0[24Ł "1 s\ 2!Me1#\ 0[46 ð0[23Ł "ddd\ J  02\ 8\ 1 Hz\ 8?!
H#\ 0[59\ 0[56 ð0[51\ 0[55Ł "1 s\ br[\ 00!Me1#\ 0[89 ð0[67Ł
"dddd\ J  01\ 5[4\ 2\ 1 Hz\ 7!H#\ 0[84 ð0[46Ł "qdd\ J  6\
6\ 2 Hz\ 09!H#\ 1[93 ð1[49Ł "d\ br[\ J  05 Hz\ 5!H#\ 1[14
ð1[04Ł "dd\ J  06\ 2 Hz\ 0!H#\ 1[15 ð1[08Ł "d\ br[\ J  01
Hz\ 7?!H#\ 1[40 ð1[87 "d\ br[\ J  05 Hz\ 5?!H#\ 1[76 ð1[69Ł
"dd\ J  06\ 6 Hz\ 0?!H#\ 3[80\ 4[09 ð3[83\ 4[91Ł "1 s\ 3!
CH1#[ 02C!NMR] see Table 09[ GCÐMS "HP#] m:z ")#
135 "M¦\ 099#\ 120 "07#\ 107 "24#\ 192 "52#\ 089 "15#\
078 "08#\ 065 "44#\ 064 "58#\ 052 "18#\ 051 "21#\ 050 "84#\
036 "44#\ 024 "26#\ 023 "37#\ 022 "099#\ 010 "24#\ 008 "55#\
097 "34#\ 096 "73#\ 094 "55#\ 82 "54#\ 80 "099#\ 68 "49#\
66 "47#\ 58 "50#\ 56 "44#\ 44 "49#\ 42 "28#[ C06H15O] calcd[
135[0873\ found 135[0889 "HRÐMS#[
Copyright Þ 1999 John Wiley + Sons\ Ltd[
POLAR FRACTION OF HAITIAN VETIVER OIL 056
00\01\02!tri!nor!7\7!Dimethyleudesm!4!en!6!one
ð"3SR\7SR#!2\2\3a\7!tetramethyl!3\3a\4\5\6\7!
hexahydro!1"2H#!naphthalenone\ 05#
GC] 74)[ IR] 0569\ 0519 cm−0 "C1C0CO#[ 0H!NMR]
d 0[96 "d\ J  5[4 Hz\ 3!Me#\ 0[01 "s\ 7!Me#\ 0[01 "dddd\
J  02[4\ 02\ 02\ 3 Hz\ 2!Hax#\ 0[08 "s\ 09!Me#\ 0[20 "s\
7!Me#\ 0[27 "ddd\ J  03\ 02[4\ 3[4 Hz\ 0!Hax#\ 0[48 "d\
br[\ J  02[4 Hz\ 1!Heq#\ 0[55 "d\ br[\ J  03 Hz\ 0!Heq#\
0[61\ 0[64 "1 d\ J  03 Hz\ 8!H1#\ 0[67 "ddddd\ J  02[4\
02[4\ 02[4\ 3\ 3\ Hz\ 1!Hax#\ 0[89 "d\ br[\ J  02 Hz\ 2!
Heq#\ 1[30 "dqddd\ J  02\ 5[4\ 5[4\ 0[4\ 0[4 Hz\ 3!H#\
4[60 "d\ J  0[4 Hz\ 5!H#[ 02C!NMR] d 07[2 "q\ 3!Me#\
10[4 "t\ C!1#\ 14[6 "q\ 09!Me#\ 16[0\ 16[4 "1 q\ 7!Me1#\
23[9 "d\ C!3#\ 25[5 "s\ C!09#\ 26[9 "t\ C!2#\ 30[9 "s\ C!7#\
32[4 "t\ C!0#\ 41[3 "t\ C!8#\ 008[1 "d\ C!5#\ 060[7 "s\ C!4#\
194[4 "s\ C!6#[ GCÐMS "HP#] m:z ")# 195 "M¦\ 09#\
049 "099#\ 024 "41#\ 011 "7#\ 010 "7#\ 097 "03#\ 096 "09#\
094 "4#\ 82 "7#\ 80 "00#\ 68 "09#\ 66 "7#[ C03H11O] calcd[
195[0560\ found 195[0561 "HRÐMS#[
00\01\02!tri!nor!7\7!Dimethyleudesma!2\4!dien!6!one
"06#
GC] 54)[ 0H!NMR] d 0[03 "s\ 7!Me#\ 0[10 "s\ 09!Me#\
0[29 "s\ 7!Me#\ 0[36 "ddd\ br[\ J  01\ 01\ 4[4 Hz\ 0!Hax#\
0[46 "dd\ br[\ J  01\ 4[4 Hz\ 0!Heq#\ 0[60\ 0[66 "1 d\
J  03 Hz\ 8!H1#\ 0[73 "dddd\ J  0[4\ 0[4\ 0\ 0 Hz\ 3!
Me#\ 1[07 "ddddq\ J  19\ 4[4\ 4[4\ 0[4\ 0[4 Hz\ 1!Heq#\
1[26 "ddddq\ J  19\ 01\ 4[4\ 2\ 0 Hz\ 1!Hax#\ 4[71 "s\ 5!
H#\ 4[88 "ddqd\ J  4[4\ 2\ 0[4\ 0 Hz\ 2!H#[ 02C!NMR]
d 08[6 "q\ 3!Me#\ 12[0 "t\ C!1#\ 13[1 "q\ 09!Me#\ 17[0\
18[2 "1 q\ 7!Me1#\ 22[5 "s\ C!09#\ 26[9 "t\ C!0#\ 30[0 "s\
C!7#\ 40[4 "t\ C!8#\ 008[6 "d\ C!2#\ 020[0 "s\ C!3#\ 023[4
"d\ C!5#\ 051[9 "s\ C!4#\ 194[5 "s\ C!6#[ GCÐMS "HP#]
m:z ")# 193 "M¦\ 02#\ 078 "0#\ 065 "1#\ 050 "7#\ 037
"099#\ 022 "23#\ 008 "09#\ 094 "24#\ 80 "00#\ 66 "7#\ 58 "1#\
54 "2#\ 42 "1#[ C03H19O] calcd[ 193[0403\ found 193[0404
"HRÐMS#[
Results
The transformation of the polar alcohols to the methyl
ethers was performed with the intention to cleave them
to the corresponding alcohols[ However\ all attempts in
this direction\ either with BBr2 15 or trimethylsilyl iodide
"TMSI#\16\17 failed[ Therefore\ the structure of the ethers
M was determined as such[ The 0H! and 02C!NMR data
of the methyl ethers are nearly identical with those of
the alcohols * with the exception of the CHn!OR
group * as demonstrated with compounds 09:M 09\
13:M 13\ 15:M 15\ 29:M 29\0 27:M 27\ 39:M 39 and
30:M 30[ Conclusively\ the alcohols corresponding to
the methyl ethers are in fact constituents of vetiver oil[
The methyl ether fraction VM "constituents see Table
1# was prepared from a medium polar to polar fraction
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
057 P[ WEYERSTAHL ET AL[
V 2 of the vetiver oil[ Split!tube distillation of VM
gave 24 fractions "9[4Ð1[4 g each#\ some of which were
further separated by repeated FC[
Eudesmane derivatives (Scheme 2, Table 3)
The methyl ethers M 13 and M 14 of vetiselinenol 13
and its C!00 epimer 14 are main constituents of fraction
VM[ The 0H!NMR data of M 13 are in good agreement
with those of "−#!vetiselinenol 13[6\7 Yoshikoshi et al[6
and Andersen7 isolated the 09!epi!eudesmadienol 13
from vetiver oil and determined its absolute con_gur!
ation[ Additionally\ Andersen7 demonstrated that "¦#!
b!eudesmol 11 and elemol\ present in vetiver oil\ have
the normal 6b!isopropylÐ09b!methyl con_guration\
whereas "−#!junenol "eudesm!3"04#!en!5b!ol#18 has the
6a\09aÐdi!epi con_guration[
The structure of a second methyl ether M 07 cor!
responded to the known {"−#!iso!vetiselinenol| "07#[5
The 1!methoxy group is in an equatorial position due
to the coupling constant of 01 Hz of 1!H with 0!H[
According to the 0H! and 02C!NMR data\ a third
methyl ether\ M 6\ also exhibited a eudesma!3"04#\6!
diene skeleton[ Decoupling experiments and the NOED
spectra showed an axial methoxy group on C!2 "2!H] d
2[69\ dd\ J  2 and 2 Hz#[ Since the absolute con!
_guration of M 13 is known6\7 we suppose that M 6 and
M 07 have the same 09!epi!eudesmane skeleton "09a!
Me#[
The 0H!NMR spectrum of methyl ether M 15 was
very close to that of alcohol 15\ which was isolated
previously from Hedychium `ardnerianum Roscoe8 and
Sideritis varoi[29 The coupling constants of 0!H "d 2[90\
dd\ J  09 and 5 Hz# and 6!H "d 1[97\ dd\ br[\ J  00
and 2 Hz# indicated an equatorial arrangement of both
Scheme 2.
Copyright Þ 1999 John Wiley + Sons\ Ltd[
the 0!methoxy and 6!isopropyl group[ Because the
direction of optical rotation of methoxy compounds
usually is the same as that of the corresponding alcohols\
we presume to have isolated the enantiomer of the
known alcohol 15 "reference 29] 15] ðaŁD −6>^ M 15]
ðaŁD ¦13>#[
Eremophilane derivatives (Scheme 3, Table 4)
A further main constituent of fraction VM is the methyl
ether M 30 of the known "¦#!isovalencenol "30#[
Although alcohol 30 is a main component of Haitian
vetiver oil\ and although rac!30 was synthesized\20 only
some 0H!NMR values are available[ 0H! "CDCl2\ C5D5#
and 02C!NMR data of the isolated compounds 30 and
M 30 proved to be nearly identical[
The methyl ether M 27 exhibited 0H!NMR data simi!
lar to those of the main product 27 obtained on LiAlH3
reduction of nootkatone[21 NOED spectra con_rmed
the equatorial position of the 1!methoxy\ 3!methyl and
6!isopropenyl group\ as well as the axial 4!methyl group
of nootkatyl methyl ether M 27[ Recently\ 1!epi!noot!
katol A\ possessing calcium!antagonistic activity\ was
found in the fruits of Alpinia oxyphylla Miquel[00
Isonootkatol 39 was identi_ed as a main constituent
of the medium polar to polar fraction V 2[ The structure
was unequivocally determined by MnO1 oxidation of
39 to yield the known isonootkatone "a!vetivone\ B#[09\22
Likewise\ fraction VM contained isonootkatyl methyl
Scheme 3.
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
 POLAR FRACTION OF HAITIAN VETIVER OIL 058

ether M 39[ Both the 1!hydroxy and the 3!methyl group

of M 39 are in an equatorial position\ because one of
the protons at C!2 "d 0[23# shows two large coupling
constants with one of each neighbouring protons
"J1\2  09\ J2\3  02 Hz#[ The con_guration was
additionally proved by the NOE of the axial 1!H "d
2[76# with the axial 3!H "d 0[45#[
A fourth methyl ether M 20 "C05H15O\ HRÐMS
123[0881# could not be separated by FC from M 30[
Subtraction of the 0H!NMR values of M 30 in the
spectrum of the mixture and decoupling of the remain!
Ž
=
ing signals established a sequence 0C1CH!
Ž
=
0CH"OMe#0CH10C1CH1[ The coupling constants
J  09\ 4[4\ 1 and 1 Hz and the chemical shift "d 2[68#
of the CH!OMe signal where nearly identical with those
of M 27 and M 39[ Irradiation of the signal at d 0[39
led to collapsing of the two methyl doublets at d 9[76
and 9[78\ and revealed the existence of an isopropyl
group[ The 02C!NMR values indicated similarities to
those of M 27[ Although an 0H02C!correlation was not
possible\ we propose structure M 20 given in Scheme 2[
The axial position of the 4!methyl group "d 0[12# was
ascertained by its strong NOE with the axial 2!H "d
1[25#[

Guaiane derivatives (Scheme 4, Table 5)

Repeated FC on basic alumina eluted after the methyl
ethers of zizaenol "M 08:M 10#\ b!funebren!03!ol "M
02#0 and prezizaen!2!ol "M 03#\ a new ether M 00
"C05H15O\ HRÐMS 123[0889#[ A secondary methoxy
group was recognized by the 0H!NMR signals at d 2[20
"s# and d 2[31 "ddd\ J  6\ 2 and 1[4 Hz#[ The signals at
d 9[87\ 0[99 "1 d# and d 0[60 "dd#\ 3[51\ 3[56 "qd and dd#
revealed one isopropenyl and two methyl groups[ The
02
C!NMR spectrum showed a disubstituted and a tetra!
substituted double bond^ the values of C!4 to C!02 and
C!04 "09!Me# were nearly identical with those of a!
guaiene "C#[02 The other 0H! and 02C!NMR assignments
for the established guaia!0"4#\00!dien!2!ol structure M
00 were made by detailed analysis of the 0H0H! and
0 02
H C!COSY and NOED spectra[ The seven!membered
ring of M 00 exists in a boat conformation according to
the NOED spectra and PCMODEL23 calculations[
FC of a high!boiling fraction "b[p[ 55Ð56>C:9[91
mbar# yielded the known pogostol "22#\ which was pre!
viously isolated from patchouli oil "Po`ostemon cablin
"Blanco# Benth[# by Hikino et al[ "0857#24 and later
"0873# by Itokawa01 from Alpinia japonica "Thunb[#
Miquel[ Itokawa formulated the relative ster!
eochemistry of 22\ based on the assumed con_guration
of guaiene epoxide D[ The 02C!NMR values of 22 are
identical with those given in reference 01\ the relative
con_guration was now ascertained by the NOED spec!
Scheme 4.
tra[ Epoxyguaiene D itself was isolated some years ago
from Vietnamese agarwood "Aquilaria a`allocha#[03
A new sesquiterpene alcohol\ 33 "C04H15O\ HRÐMS
111[0875#\ was obtained by FC of a medium polar veti!
ver oil fraction containing mainly khusimone "F#[ The
0
H!NMR spectrum exhibited signals of one methyl
doublet at d 9[884 "d\ J  6 Hz#\ one methyl singlet "d
0[01#\ an isopropyl group "d 0[99\ 0[91\ 1 d^ 1[18\ qq#
and one ole_nic proton "d 4[33#[02C!NMR signals at d
011[1 "d#\ 038[0 "s# and 62[6 "s# con_rmed the existence
of one trisubstituted double bond and one tertiary alco!
hol group[ Spin decoupling and 0H02C! correlation indi!
cated a guaiane skeleton[ The relative con_guration of
cis!guai!5!en!09!ol "33# was established by detailed
analysis of the NOED spectra[ Strong NOEs of 4!H "d
1[70# with 0!H "d 1[08#\ 3!H "d 1[95# and 7?!H "d 1[22#
determined the cis!arrangement of both rings and a boat
conformation of the cycloheptene ring[ Furthermore\
an energy!minimized PCMODEL23 calculation sup!
ported a boat conformation of the cycloheptene ring of
33 with a distance of 1[3 _ between 4!H and 7?!H[
Salvialane derivatives (Scheme 5, Table 6)
A compound M 7 "C05H17O1\ HRÐMS 141[1981#\ more
polar than most of the other methyl ethers\ showed 0H!

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062
069 P[ WEYERSTAHL ET AL[

Scheme 5.

NMR signals of one methyl singlet "d 9[86#\ one!low

_eld shifted methyl singlet "d 0[16#\ an isopropyl group
"d 9[71\ 9[78\ 1 d\ 0[27\ qqd# and a methoxy group
"d 2[20#[ The 02C!NMR spectrum displayed no C1C
double bond signals[ Singlets at dc 68[9 and 009[0 made
an ether and an acetal function obvious[ Therefore\
this must be a tricyclic compound[ Detailed analysis of
the0H0H! and 0H02C!COSY\ HMBC and NOED spectra
corroborated the salvialane skeleton of M 7[
Solvolysis of acetal M 7 with Amberlyst 04þ in ace!
tone furnished hemi!acetal 7\ the 0H!NMR data of
which are nearly identical with those of M 7 except of
8b!H\ which is ca[ 9[6 ppm low!_eld shifted due to the
neighbouring 09b!OH group[ The MS of 7 and M 7
show m:z 012 "C8H04] 0!methyl!2!isopropylcyclo!
pentene=¦# and m:z 70 "C5H8] 0!methyl!cyclopentene=¦#\
typical of salvialane derivatives "e[g[ mint oxide\ mint
ketone25# as main fragments[ Scheme 6.

Prezizaane, nor-zizaane and zizaane derivatives

(Scheme 6, Table 7)
An ether M 03 "C05H15O\ HRÐMS] 123[0877# could not
be separated completely from zizaenyl ether M 08 "see
Figure 0#[ The 02C!NMR values were close to those of
M 08 and prezizaen!01!yl methyl ether "M 18#[0 Fur!
thermore\ the 0H!NMR spectrum revealed two doublet
signals of the methylene group "d 3[55\ 3[60\ 1 d\ J  0[4
Hz# and a doubletÐdoublet "J  5[4 and 3[4 Hz# at d
1[79 "7!H#\ typical of a prezizaene skeleton[ The coup!
ling pattern "ddd\ J  6\ 5[4 and 1[4 Hz# of 2!H "d
2[22# corresponded to that of 2b!H in M 08[ 0H02C!
correlation and the NOED spectra _nally led to the
formulation of a prezizaen!2a!yl methyl ether "M 03#[
A mixture of two methyl ethers "C04H13O\ HRÐMS]
119[0712# was isolated from a low boiling fraction "b[p[
32>C:9[91 mbar# of VM[ According to the 0H! and 02C!
NMR data\ these compounds were formulated as the
epimeric "at C!1# 01!nor!zizaen!1!yl methyl ethers M 1
and M 2[ The structure of M 2 "with 1a!OMe group#
was unequivocally con_rmed by NaBH3 reduction of
khusimone F\ furnishing mainly "75)# 01!nor!zizaen!
1a!ol "2#\26 with 0H! and 02C!NMR data very close to
those of M 2[ The con_guration was again deduced
from the NOED spectra[ The signal of 4b!H "d 1[62# in
the 0H!NMR spectrum of M 1 is 9[25 ppm low!_eld
shifted in comparison to that of M 2 "d 1[26#\ due to the
syn!standing 1b!methoxy group[ On the other hand\
shielding by the syn!standing CH1 group "C!09# gives
rise to a high!_eld shift of about 9[2 ppm for 1a!H "d
2[27# of M 1[
Another nor!zizaene "C03H19O\ HRÐMS] 193[0407#
was isolated from a weak polar fraction of the vetiver
oil\ containing 0\09!epoxy!amorph!3!ene3 and kessane
"E#[05Ð07 0H! and 02C!NMR data were similar to those
of khusimone "F#\0 but * instead of the signals of the
CH1C1O group * signals of an epoxide "dH 2[19\ 2[28\
1 d\ J  2 Hz^ dc 59[1\ 43[5\ 1 d# were observed[ There!
fore\ a 01!nor!1\2!epoxyziza!5"02#!ene "34# was for!
mulated[ The con_guration was ascertained from the
NOED spectra[
Two compounds\ belonging to the main constituents
of VM\ were easily identi_ed as zizaen!2a!yl "M 08#
and !2b!yl methyl ether "M 10# because the 02C!NMR
data were close to those given for the corresponding
zizaen!2!ols 08 and 10[08 Zizaenol 08 has been known

Copyright Þ 1999 John Wiley + Sons\ Ltd[ Flavour Fra`r[ J[ 1999^ 04] 042Ð062

as a vetiver oil constituent since 0869[6\7 For comparison
purposes\ the 1!epi!zizaen!2!ols 35 and 36 were prepared
by NaBH3 reduction of 1!epi!zizaen!2!one[0 As
observed with the zizaenol pair 08 and 10\ the trans!
arrangement of the 1!methyl and 2!hydroxyl group in
35 e}ects a down!_eld shift of the 02C!NMR signal of
the 1!methyl group "d1!Me 08] 06[9^ 10] 00[9^ 35] 01[0^ 36]
7[9#[ The syn!standing 2b!OH group of 35 exerts a
down!_eld shift of 9[3 ppm on the 0H!NMR signal of
4b!H "d4b!H 35] 1[60^ 36] 1[20#[
The main constituent of VM\ khusimyl methyl ether
M 29\0 was used to try the methyl ether cleavage\ but
treatment with BBr2 15 gave only the isomerization prod!
uct isokhusimyl methyl ether "M 37# and starting
material[ Reaction with trimethylsilyl iodide "TMSI#16\17
a}orded a mixture of khusimyl iodide and M 29[ No
further attempts have been carried out with other
methyl ethers[
Khusiane (syn. helifolane or allo-cedrane)
derivatives (Scheme 7, Tables 8 and 9)
"−#!Khusian!1!ol "09# is a known constituent of vetiver
oil[19 It was isolated from a medium polar fraction of
the oil[ The 0H! and 02C!NMR data are identical with
those of "¦#!allo!cedrol "ent!khusian!1!ol# found in
Juniperus ri`ida Sieb[ et Zucc[\10 Biota orientalis10 and
the liverwort Porella navicularis Lindb[11 The 0H! and
02
C!NMR data of the corresponding methyl ether M
09\ isolated from fraction VM\ were nearly identical
with those of 09[
A methyl ether fraction containing eudesmadienyl
ether M 6 and khusimyl ether M 29 exhibited in the 0H!
Scheme 7.
Copyright Þ 1999 John Wiley + Sons\ Ltd[
POLAR FRACTION OF HAITIAN VETIVER OIL 060
NMR spectrum additional signals of a third constituent
M 01 with ole_nic signals "d 4[73\ 5[25\ 1 d\ J  7[4 Hz#
typical of helifolene derivatives[12\27 The proposal of this
skeleton was supported by three methyl singlets "d 9[64\
9[73\ 0[91#[ Instead of the 6!methyl doublet\ emerging
in the helifolene spectra\ a methoxymethyl group "d
2[08\ 2[34\ 1 dd^ 2[23 s# was present[ The con_guration
of M 01 corresponded to that of helifolene D "49#[12
The assignment of the structure and stereochemistry of
helifolen!03!yl methyl ether "M 01# was con_rmed on
the one hand by comparison of the 0H! and 02C!NMR
data "see Table 8# and\ on the other hand\ by the NOED
spectra] 1!H "d 4[73# gave a strong NOE with 2!Me "d
0[91#\ 0!H "d 5[25# with one 01!H "d 2[34#\ 00!Meexo with
09!Hexo\ and 00!Meendo with 3!Hendo and both 8!H[
Spirovetivane derivatives (Scheme 8, Table 10)
A new methyl ether M 31 was identi_ed in a mixture
"0 ] 0# with isovalencenyl ether M 30[ The 02C!NMR
spectrum indicated one tri! and one tetrasubstituted
double bond\ a methoxymethyl group and a low_eld
shifted singlet\ d 37[5\ typical of an acorane or vetivane
skeleton[ Signals of one methyl doublet\ two allylic
methyl groups\ an ole_nic proton and an isolated\ low!
_eld shifted AB system "d 1[13\ 1[18\ J  05 Hz# were
recognized in the 0H!NMR spectrum[ Due to the latter\
an acorane skeleton was excluded[ According to the
0
H! and 02C!NMR data\ a spirovetiva!2\6"00#!dien!01!
yl methyl ether "M 31# was most likely[
Furthermore\ the structure was corroborated by the
spectral data of an aldehyde 40\ which was isolated after
MnO1 oxidation of the polar vetiver oil fraction V 2\
followed by repeated FC of the product[ Conclusively\
spirovetivadienol 31\ again obtained by NaBH3
reduction of 40\ is a constituent of vetiver oil[ An alde!
Scheme 8.
Flavour Fra`r[ J[ 1999^ 04] 042Ð062
061 P[ WEYERSTAHL ET AL[
Scheme 9.
Scheme 10.
hyde G with a structure similar to that of 40 was isolated
recently from agarwood oil "Aquilaria a`allocha
Roxb[#[13
Artefacts (Schemes 9 and 10, Table 10)
Two derivatives of b!vetivone "41# were isolated from
fraction VM[ M 28\ the enol ether of b!vetivone "41#\
and M 32\ formed by dimethylation of the b!vetivone
enolate anion and subsequent O!methylation\ were eas!
ily identi_ed by comparison of their 0H! and 02C!NMR
data with those of b!vetivone "41#[ Hydrolysis of M 32
with Amberlystþ 04 a}orded ketone 42[
00\01\02!Tri!nor!eudesm!4!en!6!one is a known con!
stituent of vetiver oil^0\25 the 7\7!dimethylated derivative
05 was identi_ed in fraction VM[ 0H! and 02C!NMR
spectra revealed the presence of a second derivative\ the
dienone 06[ According to the 0H!NMR data a dimeth!
ylated nor!eremophiladienone with double bonds in
positions 2\3 and 8\09 could be excluded\ since only
signals of two low!_eld shifted protons "d 1[07\ 1[26#
appeared
Sesquiterpene alcohols (Scheme 11)
Some tertiary alcohols were isolated from fraction VM[
Besides "¦#!b!eudesmol "11#\ valerianol "12# and "¦#!
Copyright Þ 1999 John Wiley + Sons\ Ltd[
Scheme 11.
amorph!3!en!09!ol "17#\ known constituents of vetiver
oil\3\6\7 pogostol "22#\ described above\ was also ident!
i_ed[ Eudesm!5!en!3!ol "04#\ a constituent of Abies
alba28 and A`eratina saltillensis\39 exhibited 0H! and 02C!
NMR data identical with those given for synthesized
rac!04[30 The spectral properties of a!eudesmol "16#\ of
"¦#!intermedeol "23#31\32 and of eudesm!6"00#!en!3!ol
"juniper camphor\ 26#33 agreed with those of authentic
compounds and those reported in the literature[
Odour
Arctander35 gives the following description of the odour
of vetiver oil "{Bourbon type|#] {sweet and very heavy
woody!earthy\ reminiscent of roots and wet soil\ with a
rich undertone of {{precious wood notes|| |[ The inves!
tigated oil evolved fresh woody\ camphoraceous\ minty!
fruity top notes\ the heart notes were strong warm!
woody\ vetiver!\ ambra!\ cedar!\ khusimone!\ grape!
fruit!like[ The medium polar to polar fraction V 2 of
the oil was evaluated as warm!woody\ sandalwood!like\
sweet\ sour\ grapefruit!like\ typical of vetiver oil[ The
methyl ether fraction VM smelled warm!woody\ greasy\
metallic\ grapefruit!like\ dusty\ ~owery\ spicy\ anise!\
khusimone!like\ typical of vetiver oil[ Olfactory evalu!
ation of some isolated methyl ethers "M 13\ M 15\ M
Flavour Fra`r[ J[ 1999^ 04] 042Ð062

27\ M 30 and\ in particular\ M 29# showed that even
after methylation the typical vetiver notes "warm!
woody\ grapefruit# were maintained[ This observation
reminds to the fact that the commercial derivatization
of vetiver oil to give {vetiveryl acetate| improves the
valuable vetiver notes "woody\ fruity#\ under!sup!
pressing the undesired tonality of wet soil[
Acknowled`ements * We thank Dr H[ Surburg\ Haarmann + Reimer
GmbH\ D!26590 Holzminden\ for the vetiver oil and for the olfactory
evaluations[
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Copyright Þ 1999 John Wiley + Sons\ Ltd[
POLAR FRACTION OF HAITIAN VETIVER OIL 062
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