Professional Documents
Culture Documents
Reprinted
fromPerfumer
& Flavorist,
November/December
1998,Vol.23, No.6, P. 35
225
Hethelyi et al. (1995) analyzed essentialoils prepared
Table ll. Percentage composition of from O. basilicatnnative to Hungary' They compared these
Italianbasil aroma comPounds oils with those available commercially and found that three
(80-907o);
tlpes could be distinguished:oils rich in linalool
Compound 12 34 (ca. 60Vo)with some methyl chavicol
.riL .i"h in linalool
1. O 7 8.69 3.96 ( 0 7o
(5 -l}Eo),geraniol (5 - 10 7o) and eugenol 5 - 1 ) ; and oils rich
(E)-2-hexenal
(Z)-3-hexenal 0. 28 0. 02 0 .0 4 0.15 in both liialool (33-15Ea)and methyl chavicol (33-457o) In
0. 11 3. 64 basil oils
benzaldehyde addition, the authors noted that all Hungarian
o.42 0.87
possessedy-muurolene (I.00-4.67o),which accounted for
l./J
ct-prnene
2.28
1-octen-3-ol 0.90 5.47 4.79
ihe special' aromatic fragrance. Furthermore, they- found
0.86 5.20 4.04
B-pinene that most of the imported-basil oils contained methyl chavicol
myrcene 0.66 3.57
(80-937o).
phenylacetaldehYde 0. 29
10.22
PetropoulosandVlachou (1995) analyzedthree cultivars
7.70 30.44 31.15 'sgouros' and
1,8-cineole
1. 65 0. 43 3.24 0.97 of basil grown in Greeceand known as'Kinos',
ocimene* 'Mauroirytikos'. They were found to contain the following
inalool 20.41 17.89 21.84 43.07
camphor 1. 09 0. 43 3.24 0.97 major constituents:
'Kinos': 'Mauromytikos':
2-methylene-6-methYl-
0. 41 0. 95 linalool(54.4%) methylcinnamale (37.8%)
7-octen-2-oll
bicyclo eugenol(7.3%) linalool(22.6%)
1,7,7{rimethyl
0.48 1. 04 methylchavicol(29.9%) 1,8-cineole(7.9%)
[2.2.1]hepten-2-olt
camphor(t)
p-menth-3-en-2-ol1 0. 12
2,2,4-trimethYl-3- 'Sgouros':
-
cyclohexene-1 linalool(41.0%)
methanolt 3.22 0.42 3.34 methylchavicol(13.0%)
1,7,7trimethYl-bicYclo geraniol(9.0%)
[2.2.1]heptan-2-Yl camphor(t)
acetatet 0.51
eugenol 28.19 Luo rg.rg t = trace (< 0.'l%)
Compound TypeA oil TypeB oil Compound Type A oil TypeB oil
d-prnene 0.27-0.78 0 .0 8 -0 .19 h ^ r n \r l .^ a f.+6 I 0-0.25
cxthujene r-0 .1 8 t cr{enchol 0-t 0-1 . 35
campnene t-0.32 0 .0 7 -0 .18 + p-elemene
B-caryophyllene 7.26-12.63 2.84-5.09
B-pinene 0 .1 3 -1 .3 0 0 .1 0 -0 .21 terpinen-4-ol t
sabinene 0-0.56 t-0 .1 6 cr{arnesene* 1.00-5.48
6-3-carene 0
0 -0 .1 s-humulene 0.08-0.22 r-o.so
cr-phellandrene 0 -0 .1
6 I methylchavicol 0.37-12.33 0.21 - 7. 87
myrcene 0.24-0.92 0 .2 3 -1 .58 (E)-B{arnesene t-0.72
d-terpinene 0 .11 -0 .3 0 t-0.06 (Z)-B{arnesene 0.16-1
.67
limonene 0.34-1 .01 0.19-0.42 borneol 0.27 - 1. 00
1,8-cineole 1 .3 0 -1 1 .6 8 1 .0 3 -1 . 88 0terpineol o.56-2.44 0.40 -.110
(Z)-B-ocimene t-0 .1 6 0.09-0.23 6-9uaiene 0.13-0.69 0.36-0.84
T-terpinene 0 .1 2 -0 .9 2 t-0 .1 9 a-tarninrrl a.d+a+^ 0.29-0.62
(E)-B-ocimene 0.84-2.99 1 .0 9 -4 . 05 geranial 0-1.56
p-cymene i-2.41 t-0 .1 1 cI-amorpnene 0.68-3.10 1.94-3.47
terpinolene 0.1'|-0.53 0.08-0.25 6-cadinene 0{
fenchone 0.49-3.21 B-sesquiphellandrene t-1.00
(E)-3-hexenolt 0 -0 .1 6 t-0.28 nerol 0.10-0.30 t-o.zo
1-octen-3-ol 0-t geraniol 0.12-1.39 0.24-0.89
linalooloxide. 0-t 0-t methyleugenol 0.10-40.44 0-0.67
a{enchyl acetate 0 .1 4 -0 .7 5 t-0.39 cubenol 0-0.74 0.20-1.89
campnor 0.06-0.32 nerolidol. 0-0.50 0-0.79
octylacetate I spathulenol 0-0.35 0-0.44
linalool 20.03-60.47 al.zs--zs.lz eugenol 0.64-21
.14 2.20-15.63
T-cadinol 0.54-4.87 3.28-5.23
* correctisomernot identified B-eudesmol 0-0.13
f probablyincorrectidentification
t = trace (< 0.01%)
Table fV. Percentage composition of the major components of eight varieties ol Ocimum basilicum
var.glabratum
x var.
Compound canum crispa glabratum purpurascens minimum pilosum purpurascens thyrsiflorum
. correctisomernot identified
t = t ra c e( < 0 . 1 % )
227
ern analltical techniques, Marotti's team found that the oils
contained: Table V. Percentage composition of oils produced
cr-pinene(0-0.38%) methylchavicol(0-41A0%) trom Ocimum basilicum of Vietnamese origin
camphene(0-0.74o/o) cr{enchylacelate(0-0.56%)
sabinene(0-0.38%) bornylacetate(0.18-1.03%) Hydrodistilled Microwaved Microwaved
B-pinene(0-2.00%) 6-elemene(0t) oil from fresh oil with oil without
myrcene(0-0.94%) eugenol(0-3.89%) Gompound leaves water water
o-terpinene(0-0.05%) o(-copaene (0-0.17o/o)
s-prnene 0.04
p-cymene(01) B-elemene (0.10-0.66%)
camphene 0.04
limonene(0-0.58%) cis-ct-bergamotene (0-0.16%)
B-phellandrenet 0"01
1,8-cineole (0.94-12.91%) B-caryophyllene (0.09-0.70%)
B-pinene 0.08
(Z)-B-ocimene (01) frans-d,-bergamotene (0-3.37olo)
(E)-B-ocimene (0-1.02%) 0-guaiene(0-0.27%) 7-octen-4-ol 0.17
y-terpinene (0-0.18%) cr-cadinene(0-0.36%) myrcene 0.05
p-menth-2-en-1 -ol-t cr-humulene(0.26-0.82'/.) p-cymene 0.06
(0.11-0.47%) y-muurolene (0.04-0.43%) limonene 0.01
terpinolene (1-1
.47%) germacrene D (0.72-2.1 1%)
1,8-cineole 3.39 2.24 z.a I
linalool(41.17-76.20%) germacreneB (0.50-1.30o/o)
6-3-carene 0.02
oJenchol (0-0.30'/") cx-farnesene* (0.09-0.91%)
camphor(0.10-0.83%) "y-cadinene(0.38-1.37%)
p-terpineolt 0.09 o.ou
fenchone o.87 0.37 0.40
borneol(0.21-1.21%) calamenene*(0.04-0.80'/.)
terpinen-4-ol(t-3.14%) T-cadinol(1.76-7.55o/o) linalool 2.26 2.58 2 .0 9
s-terpineol(0.12-1.1 4%) a,-fenchol 1.34 1.59 1 .2 5
camphor 1.79 1.25 | .ob
t incorrectidentiJicationbased on elution order oorneol 0.84 1.28 0.76
t = trace (< 0.01%)
o(-terpineol 0.19 0.48
Although the authors examined Blistered Lettuce Leaf, methylchavicol 58.03 04.zo 70.82
DwarfViolet Leaf, Genovese,Genovesesel.Sanremo,Giant o{enchyl acetate 0.19 0.20 0 .1 8
anisaldehyde 3.56 4.38 3.88
Genovese,Giant Violet Leaf, Lettuce Leaf, Little Green,
Little Green Compact and Napoletanocultivarswhich pos- bornylacetate 0.36 0.46 0.32
sesseda range of morphological characteristics,they con- p-propylanisole 0.19 0.22
1-(4-methoxyphenyl)-
cluded that it wasnot Dossibleto establisha strict correlation
2-propanone 0.13 0 .1 0
between morphological characteristicsand chemical com-
elemene" 1.25
position or even chemotype.
methyleugenol | -zJ 1.48 1 .4 0
The use of microwave assisted hydrodistillation was 0,27 0.33 0 .15
Bthujaplicinet
examinedby Thach et al. (1996)as a lab technique to isolate cadinene* 0.96 0.46 0.57
oil from basil grown in Vietnam. The oil produced from fresh
3-methoxy
basil leavesusing hydrodistillation was compared with oils cinnamaldehydet 0 . 5 5 7.89 6.63
produced by heating fresh basil leaves in a conventional
" correctisomernot identified
domestic microwave in a flask either with added water or
t identification
basedon incorrectcomputermatchingand elutionorder
without. After removal of the olant material. the oils were
isolated from the water by diethyl ether extraction. Oil
analysesby GC/MS yielded results that can be found in Lemberkovicset al. (1996) determined that the essential
Table V The authors also isolated an extract from the same oil content of basil grown in Hungary reached a mulximum at
lot of fresh basil leavesthat were immersed in hexane and the full flowering stage.For this strain of sweet basil, the
subjected to microwave irradiation for 4-10 min in 30-s linalool remainedthe major componentof the oil until Iatein
intervals. After separation of the plant material, hexane was the flowering at which time it decreased rapidly and the
removed and the resultant concrete was converted into an sesquiterpenecontent increased.The linalool content reached
absolute prior to its analysisalso by GC/MS. The compo- a secondmadmum at full seedripening stage;however,this
nents found in this basil absolutewere: marimum was less than that obtained at full flowerine. This
7_octen_4_otr(0.22%) borneol(1.98%) trend can be seen for the oxygenated constituenis and
mesitylenet(0.21%) cr-terpineol(1.02%) sesquiterpene hydrocarbons shown in Table VI, where the
1,8-cine ole methylchavicol(78.51%) authors give the production of oil components in terms of
6-3-carene(0.27%) bornylacelate(0.54%)
(0.19%)
milligrams per square meter.
B-terpineoll methyleu!enol (2.43%)
fenchone(0.20%) cadinene.(0.25"/.) Essential oils from nine accessionsof O. basilicum var.
linalool(4.43%) 3-methoxycin namaldehydet b asilicum, three accessions ol O. b asilia nnv ar.put-purascens,
o{enchylalcohol(1.62%) (0.37il") one accessionof an intermediate betweenvar.basilicum and
camphor(0.96%) eudesmolt(0.13%) var. purpurascens and one accessionof O. basilicum var.
*
correct isomer not identified dffirme and two Dark Opal cultivars were analyzed by
t incorrectidentificalionbased on computer-assisledMS interpretation
and/or elution order Graver et al. (1996) to determine whether the chemical
228
Table Vl. Production (mg/m2)of oxygenated compounds and sesquiterpene hydrocarbons
in sweet basil at different stages of maturity
- correctisomernot identified
I incorrectidentification
Tabfe Vff. Percentagecomposition of chemotypes of oils from 16 different accessions ot Ocimum basiticum
compositionshad any relationship between oil composition analyzedby GC and GC/MS by Venskutoniset al. (1996).
and morphologr. The authors were able to find a number of The compounds identified and the amounts in mg/kg of
different chemotlpes (Table VII). They also proposed that dried basil were determined to be:
infraspecific classification of this taxon shpuld take chemical (E)-2-hexenal (7)a myrcene(18)
characters into consideration. This was judged to be of (Z)-3-hexenol(2) octanol(t)
particular importance becausebasil is used to produce es- cr-thujene(t) o-phellandrene (1)
sentialoils. It is alsousedasa culinaryhp1b,a medicinalplant a-pinene(46) 6-3-carene(t)
camphene(3) crterpinene(1)
and an insect-controllingagent.
s a b i n e n e( 4 1 ) p-cymene(t)
A volatile concentrate of basil that was produced by 1-octen-3-ol(t) limonene(30)
simultaneous distillation and extraction (diethyl ether) was B-pinene (71) B-phellandrene (t)
229
1,8-cineole (300) anethole.(t) of basil caused only a slight reduction in the contents of
(Z)-B-ocimene (t) bornylacetate(t) methyl chavicol, 1,8-cineoleand methyl eugenol.
(E)-B-ocimene (27) thymol(40) Alio in 1996, Mizrahi et al. compared the compositionof
yterpinene(1) carvacrol(B)
eugenol(53)
oils of Argentinian cultivars of O' basilicum with those of
cls-sabinenehydrate(1)
cls-linalooloxide. (t) geranylacetate(2) imported cultivars.A summary of the compositionscan be
trans-linalool oxide- (2) methylcinnamate.(10) seenin Table VIII.
terpinolene (3) B-damascenone- (2) Lachowiczet al. (1996)comparedthe compositionof oils
crthujone(6) methyleugenol(289) oroduced from frozen fresh leavesand dried leavesofthree
lin alo ol(14 1) B-elemene(t) Lustralian basil cultivars. Although the oils from the dried
B-thujone (13) o-ionone. (t)
cr{enchol(6) B-caryophyllene (155) leaves were broadly similar to those produced from frozen
allo-ocimene- (t) BJarnesene"(49) fresh leaves,the authors determined that drying appeared to
camphor(6) trans-o(-bergamotene (t) have a significant effect on the oils in which methyl chavicol
menthone(3) o-humulene(38) was notlhe only major constituent' The reasons for the
isomenthone (t) allo-aromadendrene (t)
differences in the results obtained in this study (seeTable IX)
borneol(7) B-ionone-(18)
menthol(7) germacreneD (87) could not be explained. However, the authors did state that
terpinen-4-ol(t) germacreneB (t) the differences could not be due to the lossofvolatiles during
cr-terpineol (23) (Z)-nerolidol(16) dryrg.
methylchavicol(13385) (E)-nerolidol(5)
Lachowicz et al. (1997) compared the oil yield composi-
neral (t) caryophylleneoxide (29)
tion and supercritical extract composition of five cultivars of
geraniol(t) farnesolisomerA- (t)
geranial(t) farnesolisomerB. (t) basil grownat the OvensResearchStationin Australia'They
*correct isomer not identified
found that production of supercritical fluid CO, extraction at
a mg/kg o{ dried material 27"C/68atmos., 40"C/Bzatmos'or 40"C/150 atmos' did not
t = trace (< 1 mg/kg) change the composition of the extracts.The results of this
Furthermore, the authors found that on storage of the study are summarized in Table X.
dried basil for five and ten months, the amounts of methyl In 1997, Pasquier and Chalchat analyzedbasil oil pro-
chavicol, linalool, methyl eugenol and p-caryophyllene duced from 33 plant types ofvarious origins' In these oils,
decreased, whereas that of l,8-cineole remained fairly they characterized the following components:
constant.For example,when dried basil was stored for five campnene 1,8-cineole
months and ten months, the methyl chavicol content was B-pinene (Z)-B-ocimene
reduced IB.7%oand27.\Vo, respectively.The authors also sabinene T-terprnene
limonene (E)-B-ocimene
found that the effect of irradiation on the major constituents
Tabfe Vflf. percentage composition of Argentinian and imported oils ol Ocimum basilicum
f (E)-isomer
t = t r a c e( < 0 . 1 % )
230
Table lX. Percentage composition of basil oil produced from frozen fresh leaves and dried leaves of three cultivars
. correctisomernot identified
t = t ra c e( < 0 . 1 % )
Table X. Percentage composition of basil oils and extracts produced from Australian basil cultivars
23r
p-cymene o(-ierpineol basilicum produced from plants grown in three different
camphor germacreneD locations in Benin. The results of this study are shown in
linalool bicyclogermacrene
Table XL
e-muurotene geranial
This sameyear,Palladoet al. ( 1997)analyzeda supercritical
B-caryophyllene B-bisabolene
B-elemene nerol fluid CO, extract of ground basil leavesusing GC/MS and
frans-d-bergamotene methylcinnamate* compared it with a steamdistllled oil and a petroleum ether
terpinen-4-ol T-cadinol soxhletextract of the samelot of basil leaves.The results of
methylchavicol eugenol
theseanalvsescanbe seenin TableXII. Examinationof these
neral thymol
borneol cr-bisabolol resultswould suggestthat the basilleavesthatwere extracted
or distilledwere not homogeneousbecausethe compositions
*
correct isomer not identified were so different.
The authors found that the oils could be grouped into Also in 1997, Ravid et al. examined the distribution
those which were rich in linalool, methyl chavicol, methyl of linalool enantiomersin basil oil using chiral GC analysis.
cinnamate,1,8-cineoleand mono- and sesquiterpenehydro- In 11 of the 13 oils examined, the authors found only the
carbons. (R)-(-)-form. In two other oils,the enantiomericdistribution
Chalchat et al. (1997) also analyzed three oils of O. was:
(R)-(-)-linalool
(91-92%) (8-9%)
: (S)-(+)-linalool
o(-prnene 0 .1 0 t 0.08
Compound SCE soxE oil
o-thujene 0.03 t t
camphene 0.04 t 0,-prnene t t 0. 16
B-pinene 0.06 t 0.09 sabinene t t 0. 10
sabinene 0.03 I 0.10 B-pinene 0.14 t 0.25
1,8-cineole 4.80 1.42 0. 43
myrcene 0.20 0 .1 6 I
CI{erpinene 0 .1 0 0.08 t linalool 32.00 6.00 1 .5 5
1,8-cineole 1 .4 0 1 .5 0 2.20 campnor 0.46 I t
yierpinene 0.50 0.40 crterpineol 0.93 I 0 .16
(E)-B-ocimene 2 .3 0 0 .1 0 I methylchavicol 11.40 I 0.68
(Z)-3-hexenol 1 .5 0 6-elemene I I t
linalooloxide" 0.50 0 .' 1 0 eugenol 12-40 21.60 4.00
o,{enchylacetate 0.50 o.-07 ct-copaene 9.68 t 0.99
1 .2 0 0.20 (E)-methylcinnamate 1.40 4.40 2.50
ct-copaene
linalool +s.so 2 9 .1
0 B-elemene I r 0 .9 6
methyleugenol '1.40 t 0 .6 1
(Z,Z)-cr-farnesene 6.70 2.20 2.40
methylchavicol 1. 00 54.60 90.10 p-caryophyllene 1.08 19.80 48.70
(E)-B{arnesene 0.60 0.30 I frans-c[-bergamotene 9.60 3.00 6.76
o-humulene 0.62 0.65 6.00
(Z)-B{arnesene 0.40 0.10
bisabolene* I 1.64 t
o-terpineol 1. 80 1 .5 0 0.10
6-guaiene 0.20 0.10 y-cadinene 4.12 2.49 1.15
geranial 0.70 0 .1 0 2.10 (Z)-y-bisabolene 1 1.26 1 .1 0
tr-amorpnene 1. 40 0.60 spathulenol 0.62 t 1 .5 0
caryophylleneoxide I t 1 .2 5
s-bisabolene* 0.50
geranylacetate 0.30 cubenol 1.08 I 2.46
geraniol 0.80 0.60 cadinol- 5.79 7.86 1 8 .1 4
methylisoeugenol- 1. 70 0.08 0.10 hexadecene* t 7.53 t
nerolidol- 0.07 octadecene* I 1.80 I
232
The authors also examined the dlstribution of linalool fenchone 2,4-decadienal.
enantiomers in 11 commercial samplesof basil oil. linalylacetate
Seven 2,4-octadienal"
u.ere fbund to contain only (R)-(-)-linalool, while the terpinen-4-ol cuminaldehyde
distri_
bution in the other four sampleswas measuredto be: crs-sabinene hydrate myrtenal
frans-sabinene hydrate geranial
(R)-(-)-tinatoot
(89->99%) : (S)_(+)_tinatoot
(trace_1.1
%) o-terpinylacetate perillaldehyde
geranytacetate (E)-2-octenal
During 1997, Hasegawaet al. used GC/MS for compo_ citronellol 1-octen-3-ol
nent identification of oils produced from nine different cis-linalooloxide (furanoid) isoamylalcohol
cultivarsof basil grown in the phillppines. The composition /rans-linalooloxide (furanoid) decanol
o{ each of these oils is reported in Table XIII. The authors cis-linalooloxide (pyranoid) dodecanol
Irans-linalooloxide (pyranoid) 2-methylfuran
also examined one of the Filipino accessions(pK_2)
in butanal 2-ethylfuran
greater detail. It contained the following additional com_ heptanal methyl2-methylbutyrate
pounds for which no quantitative data wa"spresented, octanal ethyl2-methylbutyrate
Compound PK.1 PK.2 PK-3 PK-4 PK-s Lettuce Fino verde Sweet Genovese
cr-ptnene 0 .3 1 0.60 0. 1 8 0.14 0" 19 0.08 0.12
o{hujene 0.30 0 .1 3 0. 21
0.04
camphene o.07 0.90 0.03 0.06 0.05 0.03 o.o2
B-pinene 0 .6 1 0 .9 9 0.06
0.04 0.13 0.39 0.11 0.28 0.50
5-3-carene o.29 0.50 0.23 0.07 0.22 0.07 o.17
myrcene 0"54 u. c/ 0.29
0.48 0.14 o.or 0.39 0.31
a-phellandrene 0 .0 1 0.38 0.60
0.56 0.30 0.01 0.02
s-terpinene 0.02 0.02 0. 01
0.05 0. 14
0.01 0. 01
ltmonene 0 .3 1 0.53 0 .21 0.21 0.04 0.22 0.17
1,8-cineole 4.02 7. 99
0.17 0.24
3.40 1.05 0.01 4.37 1.24 3.37
(Z)-B-ocimene 0.05 0. 13 4.72
0.03 0.01 0.05 0.06
^y-terpinene 0.07 0.03 0.07
0.50 o .1 2 0.01 0.09 0.11 0.07 o.02
(E)-B-ocimene 0.79 3.25 0.66 1.99 0.08 1.24 1.28
p-cymene 0 .1 6 0.70 1. 43
0.24 0.04 0 . 1B 0.02
terpinolene 0.06 0.02 0.03
0 .1 2 0.24 o .1 2 0.10
(Z)-3-hexenylacetate r J . tc 0.15 0.11 0. 16
0.02 0. 01 0 .01 0.02 o.02 0.02 0.03
(Z)-3-hexenol 0.02 0. 01 0.05 0.01 0.03 0.01
benzaldehyde 0 .0 1 0.03 0.05
octyl acetate
o.oz
0.03 o.o7 0.02 0.13 0.02 0.14
cr-copaene 0.24 o.o7 0.37
0.08 0.06 0.06 0.04 0.06 0.11 0.13 0.11 0. 1I
campnor 0.35 0.66 0.26 0.29 0.03 0.48 0.44 0.28
linalool 22.82 0.48
3.94 2 1.0 9 0.14 \rJ./ o
octanol
o.zd 49.48 31.05 4 1.5 6
0.05 0.24 0.09 0.03 0.01 0.06 0.14 0.06 0.1 1
B-caryophyllene 4.75 7.58 4.33 4.05 4.12 4.04 6,74 4.59 9.06
methylchavicol 50.48 62.92 co .zu 82.79 0.04 35.91 0.50 39.09
neral 0 .3 1 0.65
0. 10 0.40 0.23 0.04
o-terpineol 0.01 0.05
0.54 0.72 0.52 0.42 0.03 0.64
borneol 0.54 0.56 1.1 0
0.03 0 . 15 0.16 0.06
B-cubebenst 1 .4 0 1. 07 1. 29 0.34 1.18 2.89
6-9uaiene 3.82 2.99 4.95
o .7 1 0.23 0.37 0.70
geranytacetate 1 .4 9 ' - 1.7 8
nerol 1.19 1.93 1.60 2 .2 8
0.04
geraniol o :u 0.02 1. 35 0.22 0.06 0.44
methylcinnamate* 0.12 0 .1 7
-_ f / J.03
methyleugenol 0.23 0.69 0.02
eugenol t.bv c50 1. 23
chavicol
0.06 +.so r o.r s s.5s 14-.81
0.09 0. 11 0.01 0.35 0.01 0.23 0.08
'correct isomernot identified
T rncorrectidentification
basedon elutionorder
PK-1to PK-s were plantscollectedfrom variouspartsof the
countrysidearoundcagayan de oro, Mindanao(philippines)
233
methylisovalerate caryophyllene oxide
1-octen-3-ylacetate 2-phenethyl alcohol Table XlV. Percentagecomposition of
methyljasmonate (Z)-anethole steam-distilled(SD) basil oil, a supercritical
methylepi-jasmonate (E)-anethole fluid (SF) CO, extract and a soxhlet extract
cls-jasmone 2-phenethylacetate
frans-jasmone methyleugenol SD SF
(Z)-3-hexenylbenzoate benzylalcohol Compound oil extract
2-methoxy-3-methylpyrazine methylcinnamate*
tetramethylpyrazine thymol s-pinene 0.16 t
q uin olin e anisaldehyde sabinene 0.10 t
benzylaldehyde B-pinene 0.25 0.1 4
B-damascone
methylsalicylate 1,8-cineole 0.43 4.80 t.+z
B-damascenone.
p-methoxy-acetophenone coumarin
linalool 1.55 32.00
6-dodecanolide vanillin
campnor t 0.46
cis-o[-bergamotene chavicol
ct-terpineol 0.16 0.93
trans-o(-bergamotene cinnamylacetate 1 1 .4 0
methylchavicol 0.68
cr-bisabolene* isoeugenol*
ct-numutene benzylbenzoate lavandulylacetate 0.55 0.78 I
0-cuoeDene eugenylacetate (Z)-methylcinnamate I 1.7 0 I
sJarnesene* aceticacid 5-elemene t I 1
o-guaiene propionicacid eugenol 4.00 1 2 .4 0 21.60
B-bisabolene butyricacid
acid 0-copaene 0.99 9.6 8 I
B-farnesene* 2-methylbutyric
(E)-methyl
cinnamate 2.50 1.4 0 4.40
B-santalene valericacid
isovalericacid 5-elemeneb 0.96 I I
Y-elemene 1 .4 0 t
hexanoicacid methyleugenol 0.61
6-cadinene
Y-Cadrnene heptanoicacid 48.70 1 .0 8 1 9 .8 0
B-caryophyllene
T-gurJunene octanoicacid frans-bergamotene" 6.76 9.60 3 .0 0
calamenene* decanoicacid o,-caryophyllened 6.00 0.6 2 0.65
farnesol* nericacid bisabolene* I I 1 .6 4
nerolidol. geranicacid
benzoicacid y-cadinene t. tJ 4.1 2 2.49
B-eudesmol
o,-bisabolol salicylicacid (Z)-y-bisabolene 1.10 t t.zo
ledol palmiticacid t
cubenol 2.46 1 .0 8
spathulenol myristicacid 7.86
cadinol" 18.14 5.79
hexadecenet I t 7.53
*
correct isomer not identified octadecener I I 1 .8 0
234
E. Hethe\,i, G. PtrlinkasandA. Mosonyi,Ocfutrniltasilictnressential conu n et O gratissinrurn. RivistnItril. E PPOS,(Nurnero Speciale),
oils capi-llary gas chromatographic analyses. Olaj Szappan 551-560(r997).
Kozrnetika,44(1), 21-26 (1995)
P. Pallado, G. Tassinato, M. D'Alprios and p. Traldi, Cas
C. P-etro_poukrs and A-M. Vlacho\GI.C anaLtlsi,s and.contparison Ltf chronrutographtlhnass spectronr:tiy in tLrom,a cherni,strtl: o
tlrc .flaaor of dffirent populations of bosil. In: Food Flaxori: contparison oJ e,s_sential oils unclfluxotrs exlracted by classical
generation,ana.lysisancl.pror:essinfluence.Edit. G. Charalarnbous, and.superc ritic rLlt echni ques. Rapid Cornmun. NIassSpectror-r-r.,
pp. 8,{9-E55,Elsevier Sciencell. \,'.,Arnsterdarn(19g5). rl, 1335-1341(1997).
\l Niarrga,S. Savardand B. Ilenjilali, Huiles essentielles
d,'Ocitrttnn U. Rrivid,E. Pntier.s\', I. Katzir and E. Lcwins<thn,Enantiorneric
busilicunt L. Cornposition chirnitlue et influence des zones cotrtpo,s
ttkn of linalool in the e,s
sential oilsoJ'O citnunt spt:cies ancl
climatiques surles chimiotlpes. In: Yokt.risation dcla Bioma.s,se in cnrnmerciolba.silcils. FIav. Fragr. J., f2, 293-209 (1997).
ftgetale par lcs produits naturel,s. Edits., F. X. Garneau and
Y. Hasegawa,K. Tajima, N. Toi and Y. Sugimura, Charucteri,stic
Cl. j. Collin, pp. f97-204, Actes du colloque de Chicoutirni
r:o,rrtprnents
found. in the es,sential oil of Ocintnn basilicunt L.
22-25 Aug., 1993, Centre Recherchespo,u:le Developpnrent
Flav. Fragr.I., 12, 195-200(1997).
International, Ottarva(1995).
K. W. \,Iachale, K. Nirtrnjan and V. G. Pangarkar, Rerttxenl oJ'
\I. J. Perez-Alonso,A. Velasco-Negueruela, M. l). Dura, M. d.issohed essential oils from corLclensoteiater,s of ba,sil"anil
I{armandar and J. L. Estaben,CttitltL,.sitirtn
of tlrc essentialoils l,[e.nthartn:ensi,scl.istilla.tknt.
J. Chenr. Tech. Biotechnol., 6g,
of O cinunt b asiliat n var.gLabrahtnt and Rosmarinus offi cinali,s
362-366(19e7).
fronTur:l<eq. J. Essent.Oil Res.,7,73-75 (1995',.
M. D'Alpaos, P. Traldi, G. Tassinatoand P. Pallado,Extraction of
J-C. Chalchat, R. Ph. Garry, M. Harma and L. Sidibe, PLante,s essentiuloils ondflaaours uitlt clossicarrl srtperaitittrltecltniqttr:i:
aronLatiquesrh ntlali Etude de deux Ocirtutn O. basiliamt L. et
a comltarison Rivista Ital, EPPOS, (Nurnero Speciale-Aeosto),
O. canurn Slirx. Rivista Ital. EPPOS, (Nurnero Specinle),6tE-
200-207(1997).
629 r 1 99 6)
J E. Thoppil, Contribution to tlrc stuclgoJ'esse.ntiol
oil bklsqntLrcsis R oman Ghamomi l e Oi l
in eight tarieties of Ocirntnnbasiliatnt L. Acta Pharrn.,40, f SS-
199(1ee6). In 1976, Nano et al. reportecl that an oil produced froni
\I. Marotti, R. Piccaglitrand E. Giovanelli, Diffcrences in cs.sentiol Anthemi,snobilis L. (syn.Cl.unnaemehnn nobile (L.) Allioni)
oi I conp osit io t'rof b asil ( O cirmt n b asili atn t L. ) It alian cult ix ur s contained the following cornponents:
relaterl.to nwrylnlogir:al clmracteri,stics. J. Agric. Food Chem.,
44, 3926-3929(1996). s - p i n e n e( 0 . 5 - 1 0 . 0 %) o-bulnesenel(<0.5%)
myrcene(<0.5%) 6-cadinene (<0.5%)
L. N. Thach, T. H. Anh, H. D. Tranr, D. N. T. Qu1'en,A. Loupr.,D.
B-pinene ( 0 . 5 - 1 0 . 0 %) isobutylbutyrate(0.5-10.0%)
II. Hai and L. Q. Tram, X,licrotaa..-e-assistetl.
ertracntnl process camphene(<0.5%) amylpropionate (0.5-10.0%)
of the basil oil (South\/ietnom). Tap chi Hoa hoc, 34(2), 94-98 s a b i n e n e( 0 . 5 - 1 0 . 0 %) hexylacetate(0.5-10.0%)
r | 99ti). y-terpinene (<0.5%) isobutylisovalerate (0.5-10.0%)
E. Len.rberkovics, G. Petri. H. Ngul'errand I. !Iat1i6,Relatirnt,ships s-p-dimethylstyrene (<0.5%) isobutyl2-methylbutyrate
betueat cssentialoil artd flaaoroid.Ltiosut'tthesis in sueet b asil. in: 1,8-cineole (<0.5%) ( 1 0 . 0 - 2 5 . 0 %)
Proceetlings Internatioi al St1 n qtr,.si
tr itt ) I cclici nal {s ArorruLtic pinocamphone (0.5-10.0%) 2-methylbutyl 2-methylbutyrate
Plruirts. Edits., L. E. Cral<er,L. Nolan and K. Shetty.Acta Hort., pinocarvone (10.0-25.0%) ( 1 0 . 0 - 2 5 " 0 %)
\o. 126,647-655(1996). myrtenal(0.5-10.0%) propylangelate(0.5-1 0.0%)
R. J. Cilarer. G. C. Kite, F. l. Goldstone.S. E. Brytrn,A. Paton arrd borneol(<0.5%) butylangelate(0.5-10.0%)
E. Putievs\, Iny'aspecifictnt,,t t otny ond essoni i ul oilclrcntotype.s pinocarveol* (<0.5%) isobutylangelate(0.5-10.0%)
irt su:eetbtril, C)r:inum ba.siLicun.Phytochemistry,43, 1033- myrtenol(<0.5%) isoamylangelate(ca. 25%)
1039(r9 96 ). B-caryophyllene (0.5-10.0%) 3-methylamyl angelate
0-copaene(<0.5%) ( 0 . 5 - 1 0 . 0 %)
R. Venskutonis,1,. Poll and M. Larsen, Effect of irnuliotion and.
B-copaene (<0.5%)
storugetntlLeconqtositittnofuttlrtiltconrjt,trtnisinbrtsil(Ocinu.tnt
basilicumL.). Flav. Fragr.]., 11, 117-121(1996). * correct
isomer not identilied
t tentativeidentification
I. Mizrahi, M. A. Juaez and A. L. Bandoni, DetarntirLaciondc la
conrytosiciont1calid,adde esenciasrleallt al'Laca( Ocimtn*t asilicunt In 19E3,Damiani et al. identified nine major compounds
L.) obterid,a,sde aLltixos ffictuados en Argentina. Essenze in rlore than 140 samplesof Rornan chamornile oil. They
Derir. Ag rurrr..6 6.1 49- 15,r 1996 .
{bund that the averilge percentage composition of these
K. J. l,achowicz,G.P. Jones,D. R. Briggs,F. E. Bienvenu,NL V.
componentsvaried as follorvs:
Palmer, S.S.T.Ting anclNI. Hunter,Characteristicsof es,sentirrl
oilfrcnnb asil ( Or:irrnunb asilictuttL,.)groun in Austru I io. J. Agrir.. cx,-pinene
(2.78-3.48%) butyl2-methylcrotonate
Food Chem.,44, 877-S81(i996). isobutyl
isobutyrate
(2.54- (33.07-96.79%)
4.34%) 3-decen-5-one
(8.10-8.89%)
K. J. [,acholr'icz,G.P. Jor-res, D. I1. Briggs, F. E. Bienr.enu,M. V.
2-methylbutylisobutyrate isoamyl2-methylcrotonate
Palmer,V. Misra and M. M. IIunter, Chnracteristicsof plantsand
(2.89-4.34%) (19.21-21.37%)
plant extractsfron'rfive varictiesof basil (OcigturrthasllicutttL.1
propyl2-methylcrotonate cyclodecane(1.91-2.55ol.)
grou n in Au,straltu.I. Agri c. Food Chem., 46, 2660-2665( 1997). (0.99-1.55%) (4.j 3-5.08%)
2(10)-pinen-3-one
B. Pasqrrierand J-C. Chalchat,L esbasilic,s: d)l-Trsitisnnrylrckt giclttcs
et chinitlues. RivistaItal. trPPOS, (Numero Speciaie),844-EEO When tested against :r series of 25 clif{'erentstrains of
(1ee7) bacteria, Roman chamomile was sho\ /n to possessno anti-
f -C.-Chalchat,M. Moudachirou and E. Yaf i , ContpositiorL cLtiniqttc microbial activitl' (Picczigliaet al. 1993): however, it u,:rs
tl' hu iles essenti elles d.'ori gine b dniruti se: O citrnt rn b asiliann, O. found to demonstratehigh antioxidantactivitl..
235
ei'4w's.Wir
and headspace of Roman chamomile flowers
Table XV. Chemical composition (%) of the hydrodistillate
. correctisomernot identified
t = trace (< 0.01%)
236
RueOil
Table XVl. Percentagecomposition ot the
In 1993, Zhu et al. used GC/MS to examine an oll of Ruta
volatile concentrates of different parts of
graueolens(rue) produced in Guangzhou.The compounds Cofombian rue (R. graveolens)
identified in the oil were:
4-methyl-2-heptanone 2-undecanol(0.67"t"1 Flower Leaf Stem Root
(0.25'/.) Gompound oil oil oil oil
nonylacetate(0.38%)
2-nonanone (23.17%) 2-decylacetate(O.43%) (Z)-3-hexenol 0.04 0.56 I-
2-nonanol(1.05%) 2-dodecanone (1.76o/0) 2-heptanone 0.09 0.16 I-
2-octylacetate(O.40%) 2-undecylacetate(2.75o/o) 2-octanone 0.18 1.08 0.36
2-decanone (1.34%) 2-triadecanone(0.47%) myrcene t 0.08 t-
2-nonylacetate(22.03o/o) (0.97%)
angelicin
2-undecanone (36.50%) 1,8-cineole 0.05 0.06 0.42
limonene 0.10 0.18 0.92
The following yeat Xu et al. (1994) used GC/MS to 2-nonanone 16.82 45.32 15. 19 t
analyzean oil of R. graaeolens also produced in China. The nonanal 0.06 0.24 0.05
reasonfor this analysiswas that they found the oil completely 2-nonanol 0.07 0.46 I-
inhlblted the reproduction ofgrain storagepests(Rhizopertha geijerene 1.31 4.43 11.53 50.13
dominica and Tribolium castaneum) when used at a dose naphthalene 0.04 0.16 o.02
2-decanone 1.25 1.96 2.29
rate of 1000ppm. The compositionofthe oilwas determined
to be: vu r yr,l
^ ^ +r ^ ^u^Et4
a +^ +^
tE 0.16 t
2-octylacetate 0.08 0.95 0.o7
3-hexenol*(O.07o/") 2-decanone(1.31%) geijerone - 1. 08
ethylbenzene(0.02o/o) methylchavicol(0.10%) 2-undecanone 68.05 31.12 48.43 1.93
2-heptanone (0.01%) octyl acetate (0.21%)
cr-pinene(0.O2%) 2-nonylacetate(16.71%) 2-undecanone+ 0.06 0.22 0.72
2-octanone(0.24%) 9-methyl-2-decanonet nonyl acelate 0.16 0.24
10.12%) I-
2-octanol(0.02%) 2-undecanone (36.82"/.) 2-dodecanone+ 0.91 1.68 1. 83 t
3-hexenylacetate"(0.04./") nonylacetate(0.57%) 2-dodecanone 0.68 0.84 1. 57 0. 58
2-methoxytoluene (0.02%) 2-decylacetate(0.33%) pregeijerone - 0.75
p-cymene(O.02%) 10-methyl-2-undecanonet
B-ionone - 0.07
limonene(0.09%) (1.28%) dodecylacetate 0.05 0.09 0.20 0.03
1,8-cineole(0.16%) 2-dodecanone(0.54%) 2-tridecanone+ o.12 0.12 0.05 0.02
2-nonanone (24.12%) 2-undecylacetate(3.04%)
2-nonanol(O.73o/o) 11-methyl-2-dodecanonef 2-tridecanone 1.39 0.74 1. 76 0. 52
2-octylacetate(O.48./.) (0.o7o/o) B-elemene - 0.28 I-
'1-methyl-5,6- 2-tridecanone(0.80'/") 7,8-dihydroxy-6-methoxy
diethylcyclohexenef 2,6-di-tert.butyl-4-methyl
phenol* coumann 0.08 0.01 t 0.07
(0.25o/o) (0"05%) elemol o.25 0.49 0. 57 1. 99
2-hydr oxy- 4-methoxypheny elemol(0.18%) 4-(3,4-methylenedioxy-
methylketonet (0.02"/") angelicin(0.36%) phenyl)-2-butanone 0.16 0.44 I-
9-methyl-2-nonanonef dibutylphrhalals+(0.25%) tridecane-2,4-dione - 3.01
(0.06%) phytolt(0.86%)
nonanol(O.O7'/.) 2tetradecanone 0.07 t
2-(3-phenyl-1-propyl)furant0.69 1.47 0 .1 7 t
' correctisomernotidentified methyl4-(3,4-methylene-
t compoundidentified by l\4Scomputermatching
onty dioxyphenyl)butyrate 0.19 t I-
I impurityor arti{act
psoralen 0.24 0.13 0.02
In 1995,Bourrel et al. screeneda number ofessentialoils 6-(3,4-methylenedioxy-
for their antimicrobial activifi In addition. the authors exam- phenyl)-2-hexanone 0.06 0.35 t-
ined the chemicalcompositionof eachof the oils by GC/MS. 2,4-pentadecadione - 20.26
They found that the rue oil screenedpossessedthe following 1-(3,4-methylenedioxy-
composition: phenyl)-4-hexene-3-one 0.37 2.34 2 .5 2 1 0 .6 4
2,4-heptadecadione - 0.09
myrcene(0.1%) ar-curcumene (1.0olo) 8-(3,4-methylenedioxy-
terpinolene (0.2%) zingiberene (0.4%) phenyl)-2-octanone 0.77 1.96 1 .3 9 0 .1 7
linalool("1
.9%) myristicin(0.9%)
terpinen-4-ol(0.3%) B-sesquiq!ellandrene (0.69",1 chalepensin(xylotenin) 3.09 0.94
geraniol(0.8%) (E)-nerolidol (0.8%)
thymol(0.3%) t tentativeidentification
caryophyllene oxide(2.2.k) t branchedform
2-undecanone (66.9%) cadinadienol l" (1.0%) t = trace(< 0.01%)
2{etradecanol(1.4%) lauricqpid (0.7ol.)
B-caryophyllene (1.8%) palmiticacid (1.4%)
(E)-B{arnesene (0.6%) linoleicacid (0.5%)
237
This same year, Stashenko et al. (1995) analyzed the (Z)-"y-bisabolene(0.77'k) (E)-amylcinnamicalcohol
8-cadinene(O.07o/o) (0.61%)
volatile concentratesof different plant parts of R. graaeolens
elemol(1.44%) tetradecanol(0.06%)
that was grown in Colombia. With the chosen method of (E)-nerolidol(0.26%) tetradecanoicacid (0.29%)
analysisbeing that of GC and GC/MS, the authorscompared 2tetradecanone(0.20%) curcuphenol(8.18%)
the composition of oils produced from the flowers, Ieaves, tridecanoicacid(0.07%) 2-hexadecanone(0.36%)
stems and roots. Although the oil normally encountered in y-eudesmol(0.33%) hexadecanoicacid (5.68%)
p-eudesmol(0.56%) isophytol(2.38%)
commerce is a steam distillate of the aerial parts of R.
a-eudesmol(0.42%\
graueolens,the study is of interest for comparisonpu{poses.
The results of the analysesare summarized in Table XVI. It
L-F.Zhr, Y-H. Li, B-L. Li, B-Y. Lu and N-H. Xja,Aromatic plants
is further of interest that when the authors examined the and essential constituents. South China Institute ol Botany,
various oils using a nitrogen/phosphorous detector, they ChineseAcademyof Sciences,Hai Feng Publish.Co. distributed
identified 3-pyrolidinol and l,4-dimethylpiperazine in the by PeaceBook Co., Ltd., Hong Kong (1993).
flower, leaf and stem oils. Furthermore, they determined H-H. Xu, S-F. Chiug, I. Zhov J-K. Ding and X-j. Yt, Preliminary
that the weight concentration of these nitrogenous com- studies on insecti,cidalactiaity of the rue oil antl analysis rtf its
noundsdid not exceedI x l0-47o. corwonents. Natural Product Res. Dev., 6(4), 56-61 (1994).
More recently, Pino et al. (1997) analyzedan oil of rue C. Bourrel, G. Vilarern,G. MichelandA. Gase\Etudedespropridtds
bacteriostatiques et fongistatiques en milie,u solide de 24 huiles
produced in Cuba by GC/M S.The authorsfound that the oil
essentiellesprdamblement analysdes.Rivista Ital. trPPOS., No.
contained: 16. 3-12 (1995).
myrcene(0.01%) 2-decanone(0.72%) E. E. Stashenko,H. S. Villa and M. Y. Combaiza, Comparatioe
p-cymene(0.01%) pulegone(0.10%) sndy of Colombian rue oik by hi gh resolution gaschromato graphy
lim on en e(0.1 6% ) pregeijerene(0.52%) usingdffirent futection sAstelns.J. Microcol. Sep., 7, ll7-122
(E)-B-ocimene (O.02'/.) 2-undecanone(48.67'/.) (1995), 35th Internat. Sl.mposium Chromatogr. Proceedings,
2-nonanone(0.62%) 2-dodecanone(2.43%) 475-483,Japan(1995).
camphor(0.37%) lene (0.22'k)
B-caryophyl J. A. Pino, A. Rosado and V. Fuente s, Leaf oil of Ruta graueolensL.
geijerene(1.64%) cx-humulene(0.03%) groun in Cuba.l. Essent.Oil Res.,9, 365-366(1997).
terpinen-4-ol (0.08%) 2-tridecanone(3.72'/.)
238
Progress in Essential Oils
Reprinted
fromPerfumer
& Flavorist, 1ggg,vol. 24,No.1, p. s3
January/February
239
(E,z>12
(
E ,Z-14 R = A c
\/ | \/I
a:r*o* aY*o
fffo
I ffi
)Y) "o,r.
o\
4l
..\_
n
(E,zl15 16^a -f R : i- cH5lcHr;u-,0-
cH.
1 6 S R =A c
16 h R =H
16 a- h
,'\
I ""- cooM" corv"
\ / r /'Ar.\ 6""-
[o.\/ u,YU \,\zn- Y,/:v
f(,,s-.\o oH oH
,o*",, I
't7
18 19
11
240
8-hydroxylinalyl isovalerate eicosane(t)
( 0 . 1 0 %) 8-hydroxylinalyl heptanoate
tridecylacetate(0.15%) ( 1 . 8 0 %)
heptadecane(0.70%) N-[2-(4-hydroxyphenyl) ethyl]
(E){arnesol(0.08%) tiglamide(O.20'/.)
methyl(E)-4- (E)-4-(geranyloxy) cinnamicacid
hydroxycinnamate (0.50%) ' (4.30%)
benzylbenzoate(0.06%) 8-hydroxylinalylnonanoate
B-hydroxylinalyl valerate (0.70%)
(0.09%) 8-hydroxylinalyldecanoate
B-hydroxylinalyl tiglate(0.30%) (2.20%)
tetradecylacetate(0.50%) tricosane(0.03%)
ociadecane(0.03%) N-[2-(4-prenyloxyphenyl)ethyl]
pentadecylacetate(t) tiglamide+ methyl(Z)-4-
nonadecane (0.08%) (geranyloxy)cinnamate
methylpalmitate(0.02%) (e.30%)
cozl!'le 8-hydroxylinalyl heptanoate B-hydroxylinalyldodecanoate
PO2Me
(0.30%)
J_ J (Z)-4-(geranyloxy)cinnamic
(0.30%)
methyl(E)-4-(geranyloxy)
w:v
n
Y""/> acid(1.90%)
N-[2-(4-hydroxyphenyl) ethyl]
cinnamate(6.7%)
B-hydroxylinalyltridecanoate
2-methylbutyramide (1.40%)
29 30/ (0.09%)
(
COrMe t = trace (< O.O1%)
J a-z Also in 1995, Groenewoud et al. (1995) determined that
/\
\,.v:\--
: /l^) the detection limit of propiconazole (a broad spectrum
OH bolo fungicide)was 50 ppb using GC/MS in the high resolution
JI SIM mode. Usinq this method the authors determined that
32
when boronia plants were treated with propiconazole to
QOIMe CO2Me
control rust, concretes made from flowers harvested from
J J treated plants had residual levels of 0-9.2 pp*.
\,),",,/:'\,. R. Kaiser,Netanaturalproductsof structuraland olfactoryinterest
:
OH
Y.'"/:u
OH
identifiedin figteaf absofute-(Ficus
corica L).'In: Piogressin
EssentialOils Research.Edit. E-I. Brunke,Walter de Cruyter.
33 Berlin(1986).
P.Wey_erstahl,H. Marschall,W-R. BorkandR.Rilk,Megastigmanes
\ and other constituentsof the absofuteof Boronia'metastigma
\--\ from Tasmania. LiebigsAn. Chem.,1043-1047 (f 994).
) P.Weyerstahl, H. Marschall,W-R. Bork,R. Rilk,S.Schneider and
/\
Fofo
/r^) H-C. Wahlburg, Constituentsof the absoluteof Boronia
megastigmaNeesfrom Tasmnnia.Flav. Fragr. J., 10, 297-311
(lee5).
K. M. Groenewoud,N.W. DaviesandR. C. Menarv,Deter-mination
35 ofpropiconazoleresiduein Boroniaettract (concrete).!. Agnc.
FoodChem.,43,1230-1232 (1995).
Figure 1. (continued)
24 7,11-epoxymegastigm-S(6)-en-9-one GeraniumOil
25 (E)-megastigm-7-en-3,9-dione An interestingpaper in 1992discussedthe origin ofthe rose-
26 sesquicineole scented geranium cultivars grown in India. Rajeswara Rao
27 isoitalicene and Bhattacharya pointed out that the cultivars known as
28 italiceneether (syn.6,1"l-oxidoacor-4-ene) Algerian, Tunisian and Bourbon (Reunion) were not ob-
29 methyl(Z)-jasmonate tained from imported plantsbut were selectionsmade by the
30 methyl(Z)-epi-jasmonate erstwhileCinchonaDepartment ofTamil Nadu (India) from
.r,
31 (2, trans, trans-)me\hyt2.3-di-epi-cucurbate their plantations. The one variety known sometimes as cv.
Kelkar or Indian was produced from plants imported from
32 6-jasmonicacid lactone(syn)
Reunion. The geranium known as cv. Bourbon, which is
33 (2, cis, cis-)methyl-3-cucurbater,r
grown commercially in Andra Pradesh,Karnataka and Tamil
34 (2, cis, trans-)methylcucurbate
Nadu, hasPelargoniumcapitatum(L.) LHerit ex.Aiton and
35 anti-6-jasmonic
acid lactone P,graoeolensLHerit ex. Aiton as its putative parents.
241
Using compound co-injection as the method of compo- plant material grown in Rwanda contained the following
nent identification during GC analysis,Daw et al. (1994) constituents:
found that geranium oil of Eglptian origin contained:
cr-pinene(0.03%) geranylacetate(0.33%)
B-pinene(0.06%) a-terpineol(5.87o/o) a-phellandrene (0.05%) B-caryophyllene (0.39%)
myrcene(0.20'/") citronellol(23.68%) p-cymene(0.10%) s-guaiene(0.450/4
limo ne ne(1. 17% ) geranial(5.73%) l i m o n e n e( 0 . 1 5 %) guaia-6,9-diene (3.31%)
terpinene*(1.37%) geraniol(33.50%) 1,8-cineole (0.40o/o) citronellylpropionate(0.39%)
terpinolene(0.23"/.) elem ol( 1. 61%) (Z)-B-ocimene (0.05%) geranylpropionate (1.03%)
lina loo(10
l . 14% ) linalool(3.36%) y-cadinene (0.21o/o)
frans-roseoxide{0"11%) geranylisobutyrate(0.35%)
* correct isomer not identiiied
menthone(0.23%) 6-cadinene (0.24%)
It should noted that the identification of elemol in gera- isoborneol (0.10%) citronellylbutyrate(0.18%)
isomenthone (7.49%) geranylbutyrate(0.64"/.)
nium was in error.
isomenthol(0.29%) spathulenol (0.22%)
Geranium oil produced in Kunming monthly from May to crterpineol(0.15%) furopelargone (0.10%)
October was found by Yan et al. (1994) to possessa quanti- nerol(0.22/") 2-phenethyl tiglate(1.15%)
tatively different composition. The variation in main compo- citronellol (11.41%) geranylisovalerate(0.20'/")
nents between the oils can be seen in Table I. These same neral(0.87%) 10-epi-y-eudesmol (3.23%)
geraniol(50.56%) T-cadinol(0.35%)
authors compared the composition of a geranium oil pro- geranial(2.17%) geranylvalerate(0.18%)
duced from anothercultivarthat is grown in Bin Chuangwith citronellylformate(<0.10%) citronellyltiglate(0.14'l")
oils produced in Bourbon and Morocco (seeTable I). geranylformate(0.20%) geranyl tiglate (2.49'/')
Using a procedure known as the thiobarbituric acid o-copaene(0.39%) geranyl3-methylvalerate (0.56%)
reactive substancesdetermination, geranium oil was evalu- B-bourbonene(0.54%)
ated for its antioxidant properties .,iir.g yolk, one-day-
old chicken livers or muscle from mature "gg In 1996, Ntezurubanza and Ayobanga examined the
chickens as the
medium. Although geranium oil was shown (Dorman et al. major component compositionof geranium oil produced in
1995)to possesssomeantioxidantactivity,itwas determined different regionsof Rwanda.These results are summarized
to be weak compared with the oregano, thyrne and nutmeg in Table II. The authors also compared Rwandan geraniun.r
oils. oil wlth oils produced in other parts of the world, as can be
A sample of Israeli-produced geranium oil contained seenin Table III.
cr-terpineol (0.2Ea),which was determined by Ravid et al. The sameyear, Cu (1996) reported that in Yunnan gera-
(1995) to exist in the following enantiomeric distribution: nium oil is produced in the summer (80% of production) and
winter (20Voolproduction). He also compared the compo-
(4R)-(+)-o-terpi
neol(36%): (4S)-(-)-o-terpineol
(640l.) sition of the tr,voseasonoils with an oil of Bourbon. The
The same authors found that the enantiomeric distribu- results of this comparisonare shown in Table IV
tion of a-terpineol (0.4-0.7Eo)in two commercial samples Also in 1996,Casabiancaet al. used chiral GC to measure
of geranium oil was as follows: the enantiomeric distribution of six of the imoortant con-
sl i tuentsof gerani umoi l sampl esfrom dif ler entgeogr aphi-
(4R)-(+)-oterpineol
(46-47ok)
: (4S)-(-)-a-terpineol
(53-54%)
cal regions. The results of this study are found in Table \.
A combination of GC retention indices on two caoillarv Examination of the data reveals that manv of the oils exan'r-
columns of different polaritieswas used by NtezurubJnzaet ined were probablyadulteratedwith syrthetic racemicconi-
al. (1995) to determine that geranium oil produced from pounds. In particular, the enantiomeric form of menthone
o,tq
a n d is om ent hone s h o u l d b e (+ )-me n th o n e a n d (-)- linalool(5.5%) geraniol(1O.2%)
isomenthone; ascan be seen, certain oils showed a deviation isomenthone (5.9%) yl f ormate(12.3o/o)
citronelf
menthone(0.2%) geranylformate(3.6%)
from the expected results.
citrone||ol (33.4"/.') guaia-6,9-diene (9.2%)
Lis-Balchin et al. (1996) examined the biological activig;
of numerous commercial samples of geranium oil. They A reference to the data found in Table VI should remind
found that the major components of these oils varied accord- the users ofgeranium oil that they should be very careful in
ingto origin andwithin origin, indicatingthat some ofthe oils ensuring that the oil that they purchase is authentic and
had been adulterated. A summary of the analytical results unadulterated, unlike some of the oils used in the studv bv
can be seen in Table VI. In addition, the authors further Lis-Balchinet al.
reported that an authentic sample of Australian geranium In 1997, Kaul et al. (1997a)reported that the oil yield of
oil produced from plants grown from material acquired three different cultivars of geranium grown under shade
from Bourbon (Reunion) contained the following major decreased significantly over plants grown unshaded in the
constituents: same area of India. They also found that there were some
Table ll. Percentage composition of geranium oil produced in different regions of Rwanda
Compound BGA CY KA RW MU NY KI OP M1 M2 M3
linalool 1 0 .3 12.3 7.9 7.7 12.1 6.5 7.O 7.0 3.3 u.o 2. 7
trans-roseoxide o.2 0. 8
isomenthone 6.7 4. 1 6 .1 o. l FO 4.5 7.4
citronellol eo 23.1 12.7 17.5
I O . 'J 16.7 8.8 32.0 26.3
neral 1 .2 1 .1 0.7 u.o 1.2 o.4 o.7
geraniol 40.9 qoo
42.5 52.9 43.2 62.7 18.7 19.7
geranial 3.3 2 .4 0.7 2.5 2.0 3.4 1.3 1.7
citronellylformate 4.8 :.
o, l
geranylformate o.2 1.3
geranyl acetate 0.2 u. o 0.2 0.2 0.2 0.3 1 .7
guaia-6,9-diene 1. 4 1. 7 1 .4 1.3 2.4 1.1 2.5 2.7 14.6 0.2
geranylpropionate 't.4 t.z 1 .4 2 .6 1.0 o.4 1.0 t.o 1 .9
geranylbutyrate 0.9 0. 6 1 .2 0 .5 0.8 0.6 o.2 1.0 2.4
2-phenethyltiglate 1. 9
10-epi-y-eudesmol 6.0
1. 2 1.1 u.o 1.1 no 3.1 i, 1 .3
4.7 3.7 4.2 4.5 0.5 tJ.z 8 .1
geranyltiglate 3.4 4.2 3.3 J.J 3.1 J. l 2.5 1.8 3 .0
a BG: Bugarama,Cyangugu(1100 m) RW: Rwabuye,Butare(1600m) Kl: Kivuye,Byumba(2300m) M2 and 3: Mudende,Gisenyi(2100m)
CY: Cyangugu,Mibilizi(1700m) MU: Mukoni,Butare(1700m) OP: Opynva,Ruhengeri(2100m)
KA: Karama,Kigali(1500m) NY: Nyinawinamana,Byumba(2100m) Ml: Miyove,Byumba(2100m)
243
quantitative differences in components in oils producedwith l4.9Ea)and citronellyl formate (4.37ofrom 20.37o), and an
or without shade, as shown in Table VIL increasedcontent of geraniol (22.77ofrom 8.87o)and geranyl
Some of the sameauthors,Kaul et al. (1997b)found that formate (50.07ofrom 10.07o).
menthone, citronellol and citronellyl formate contents Also in 1997, Konig et al. reported that, although chiral
of geranium oil increased significantly when it was stored GC can be used to establishthe enantiomericdistribution of
under poor conditions, while linalool, geraniol, geranyl ( +/-)-cis-rose oxide, ( +i-)-trans -rose oxide, ( +/-)-linalool,
formate and 10-epi-y-eudesmolcontents decreasedunder (+i-)-menthone, (+/-)-isomenthone and (+/-)-citronellol,
the same conditions. they cannot be used as criteria for authenticity assessment
RajeswaraRao and Bhattacharya(1997) further found
that rose-scentedgeranium plantings should be kept weed- TableVl. Comparative majorcomponent
free for the first 90 days after planting and during the last 90 composition(%)of commercial samplesof geranium
daysbefore harvesting.If the crop was not kept weed-free oil from differentgeographical
origins
during the above-notedtimes, then oil produced possessed
a decreased content of linalool (20.8Vofrom 33.37o), Chinese Bourbon Egyptian Moroccan
oils oils oils oils
isomenthone (4.87o from l2.0Vo), citronellol (1'.8Vofrom (10F (11) (21
Compound Fl
finalool 1.7-8.7 3.1-8.6 5 . 2 - 8 . 4 5 .8 0 - 1 00
TablelV. Percentagecompositionof maior isomenthone 3.1-7.0 3.4-6.7 2.9-6.1 3"8-4.5
components of Yunnansummerand winteroils
citronellol 33.3-48.5 29.7-47.7 27.5-39.8 28.9-37.8
and a Bourbongeraniumoil geraniol 4.2-18.1 7.3-17.4 13.3-19.2 15.1-18"6
c i t r o n e l l y l f o r m a t 6e . 3 - 1 1 . 6 8 . 3 - 1 1 . 6 5.8-7.9 5.5-8.1
Compound Summer oil Winter oil Bourbon oil
geranylformate 1.0-3.9 1.7-5.4 2.4-3.5 2.8-3.7
o-pinene 0.48 0.54 0.90 guaia-6,9-diene 0-6.4b 0.6.8" 0-6.7d 0-1.0"
B-p ine ne 0. 17 0. 16 0.27 10-epi-y-eudesmol0-4.3b 0-6.3" 0-6.4d 0-5.1"r
linalool 3.01 2.59 8.90
a Numberof samplesanalyzed
trans-roseoxide 1.66 1. 05 1.09
b Two Chineseoils contained1o-epieudesmol(not normallyfound in oils
cls-roseoxide 0.64 0.26 0.39 of th;s origin).Thesesame two Chineseoils did not containany guaia-
0.43 0.53 o.71 6,9-diene(a normalconstituentof Chinesegeraniumoil)
menthone c One Bourbonoil contained10-epi-Y-eudesmol (not normallyfound in
isomenthone 6. 60 6.29 9.29 oils of this origin).This Bourbonoil did not containany guaia-6,9-diene
a-terpineol 0.23 0"19 0.71 (a normalconstituentof Bourbongeraniumoil).
d Three Egyptianoils containedguaia-6,9-diene (not normallyfound in
citronellol 39.60 44.43 zo.1 |
oils of this origin)-These same three Egyptianoils did not containany
4.03 la on (a normalconstituentof Egyptiangeraniumoils).
geraniol 7.O5 10-epi-y-eudesmol
citronellylformate 12.84 15. 58 11.38 " One Moroccanoil contained1% each of guaia-6,9-diene and 10-epi-T-
eudesmol.(Guaia-6,g-diene is not normallyfound in Moroccanoil.)
geranylformate 2.10 1. 48 5.46 r One Moroccanoil containedonly 10-epi-Y-eudesmol (a normal
guaia-6,9-diene 6. 39 2.79 6.38 constituentof Moroccangeraniumoil).
Enantiomericdistribution
Compound Bourbon China Egypt Morocco Tadjikistan Tunisia
(7) (5) (3) (1) (1) ( 1)
(2S,4R)-(-)-cls-rose
oxide ot- /o 50-53 5B-59 62 61 67
(2R,45)-(+)-cls-rose
oxide 24-39 47-50 41-42 3B 39
(3R)-(-)-linalool si,5o 50 50 50 50 42
(3S)-(+)-linalool 50-69 50 50 50 50 5B
a numberof samolesanalvzed
244
becauseof the wide natural vari-
ability of constituents. Table Vll. The effect of shade on the percentage composition of
geranium oil produced from three differentcultivars
After stereochemicalslnthe-
sis of all four stereoisorrrers
cv. Kelkar cv. Bourbon cv. Algerian
of cis- and trans-rose oxide
Compound Wshade w/o shade dshade w/o shade w/shade w/o shade
ketone [ 1-(4-methyltetrahydro-
p yra n- 2- y l) - pr opan -2 -o n el , myrcene t.c 1.4 2.2 2-3 0.4 0 .3
linalool 18.5 18.1 al A
13.1 3.0
Wiirst et al. (1997) developed t.o
crs-roseoxide 0.1 0.1 0.4 0.3 t.J t.J
a method to simultaneously isomenthone 11.3 I u.o 6.8 11.6 11 .1
separateall enantiomersusing
citronellol 8.6 8.1 z t.o 20.3 43.7 45.8
a 5 0 7 o hept ak is - ( 2 ,3 -d i -O - geraniol JZ.Z 35.9 26.8 30.3 2.6 2. 2
acetyl-6-O-tert. butyldimethyl- citronellylformate 0.2 4.9 4.8 13.0
si l yl t-B - t . y c lodex t ri n i n a n geranylformate 0..t 0.2 1.6 2.2 0.4 0. 5
OV- 170 I capillary column. The 0.5 0.4
B-caryophyllene 0.5 0.3 1.4 t.o
authors applied the method guaia-6,9-diene at 2.7 0.1 0.1 1.3 t.v
of GC analysis, which also (x-numutene 1.6 1.4 5.9 6.0 0.6 0. 6
se p a r at edt he is om e ri r. ro s e 10-epi-y-eudesmol 4.6 3.9 5.9 6.0 3.2 3. 4
oxide enantiomers, to three citronellyl
tiglate 1.4 1.1 t.5 1.4 1.9 0. 3
commercial samples of gera- geranyltiglate 1.9 t.c 1.2 1.3 0.5 0. 3
nium oil. The results of this
enantiomeric study can be
found in Table VIII. Table Vlll. Enantiomeric distribution (o/dof rose
Srivastavaet al. (1997) examined the composition of oxides and rose oxide ketones in geranium oil
oils produced from two geranium chemotlpes. They found
that the oil of the first chemotlpe (obtained from Almora) Reunion Chinese Egyptian
contained: Compound oil oil oil
(2S,4R)-(-)-cts-rose
oxide 64.5 SO7 58.2
cls-roseoxide (2.35%) menthol-- (2R,aS)-(+)-crs-rose
oxide 35.5 49.3 41.B
frans-roseoxide*. o-terpineol**
QR,aR)-(-)-trans-roseoxide 62.4 49.2 58.5
menthone*" citronellol(32.26%) (2S,4S)-(+)-trans-rose
oxide 37.6 5O.B 41.s
linalooloxide-(8.68%) geraniol(0.63%)
isomenihone (6.61%) 2-phenethyl tiglate.. (2S,aR)-(-)-cls-rose
oxide ketone 62.6 50.5 57.2
linalool-- junipercamphor(9.67%) (2R,aS)-(+)-ctb-rose
oxide ketone 37.4 49.5 42.8
citronellylformate** junenol-- (2R, R)-(-)-frans-rose
oxide ketone t t r
(2S,4S)-(+)-frans-rose
oxide ketone t t r
" correct isomer not determined t = trace (< 0.1%)
.. quantitative
data not given
.. quantitative
data not given This author (Lawrence) examined the composition of
geranium oil a few years ago and determined that geranium
Mallavarapuet al. (1997)usedGC and eC/M S analysesto
oil of various origins contained the following esters:
compare the composition of oils produced separatelyfrom
ieaves,petioles and stemsof six-month-oldgeranium plants 2-methylbutylformate(t) propionate
citronellyl
raised in Hyderabad (India). The varibtion in composition citronellylformate (2.26-3.21%)
(s.97-5.30%) geranylacetate(2.95-5.12%)
betr,veenthe oils produced fiom three separateorganscan
geranylformate(2.O7-3.600/0) citronellyl
butyrate(1.93-2.62'b)
be seen in Table IX. citronellylacetate geranylpropionate
More recently,Verin et al. (1998) used GC/MS to deter- ( 1 . 0 8 - 1 . 6 5 %) (2.87-s.83%)
245
geranylbutyrate 2-phenethyl2-methylbutyrate hybrirk acclimoterl in Iunnan proaince. Fruits, 49(1), 22-23
(1.90-2.50o/o) (r-0.75%) (19e4).
citronellylvalerate geranylvalerate(t-0.37%) H.J. D. Dorman, S. G. Deans,R. C. Noble and P. Surai,Eoaluation
(0.40-0.50o/o) citronellylhexanoate(t-0.13%) of in oitro plant essential oils as notural antioxidnnts. J. Essent.
2-phenethyl propionate tiglate(t-0.82%)
citronellyl Oil Res.,7, 645-651(1995).
(0.20-0.30%) geranylhexanoate(0.10-0.53%)
geranyl2-methylbutyrate geranyltiglate(1.20-2.39%) U. Ravid, E. Putievsky and L Katzir, Determination of the
(0.40-0.50%) tiglate(0.36-1
.39%) enantiomeric cornposition of the a.terpineol in essential oils.
2-phenethyl
geranylheptanoate(1-0.07'/.\ Flav. Fragr. J., I0, 281-284 (1995).
2-phenethylisobutyrate
(0.12-0.15%) geranyloctanoate(t) L. Ntezurubanza, G. Collin, F. X. Avobangria, H. Deslauriers and
J-8. Nizeyimana,Compositionchemiqui de L'httile essentielle de
t = trace(<0.01%) Pelargoniunt grqueolens, Mentha socchalinensis,Cymbopogon
citratus et de Ocimum conum cultiadsau Rwanda.In:Y alorisation
B. R. RajeswaraRao and A. K. Bhattacharya, History andbotanical de la Biomasse adgdtale par les produits naturals. Actes du
nornenclature of rosescerted geranium cultiaars groun in India . colloque de Chicoutimi 22-25 Ang. 1993, E&ts., F-X Garneau
Indian Perfum.,36(2), 155-161(f992). and G. J. Collin, pp. 3f7-320, Centre Recherches pour le
Z. Y. Daw, G. E. El-Baroty and A. M. Ebtesam, Inhibltion of Developpment Intemational, Ottawa (1995).
Aspergillus parasiticus and growth and aflatoxin prodaction L. Ntezurubanza and F. X. Ayobangria, Perspectiuesde aalorisation
by someessentiololls. Chem. Mikrobio. Technol. Lebensmitt., rleplantes mddicinaleset ar6matiques nu Rraanda.ln:3e colloque
r6(516), (1994).
129-r35 produits naturels d'origine odgdtale,Edits., G. Collin and F-X.
D-W. Yan, Z-J. Zhang and N. Ouyang, Analysis of the chemical Garneau,pp. 37-52,Actes du colloque de Saint-Jean-sur-Richeliu,
compositiort,of essential oilsfrom scented leaaesof Pelogoniun't 18-24 Oct. 1995,Univ. Chicoutimi, Quebec (1996).
Table lX. Comparativepercentagecomposition of leaf, petiole and stem oils of lndian geranium
geranylformate 2 .6 6 1. 76 z.J I
246
J-Q. C", Geranium oilfrom Yunnan. China. Per{um. Flavor.,2 I (5 ), y-muurolene (1.89%) (2.11o/")
(E)-nerolidol
23-24 (1996). germacreneD (3.42%) spathulenol(0.86%)
H. Casabianca,J. B. Graff and S. Guillaumet, Analyses chirales et cr-longipi
nene.- (3.70./.) caryophylleneoxide (0.16%)
isotopiques de prinicpaux constihtants de roseset de gdraniums. B-selinene(0.460/o) cubenolt(0.16%)
RMsta Ital. EPPOS, (Numero Speciale),244-26I (1996). bicyclogermacrene (0.89%) epi-cubenolt(0.42o/o)
M. Lis-Balchin,S.G. DeansandS. Hart, Bioactiaityof geraniumoils cr-selinene(0.56%) T-cadinol(2.84%)
0-muurolene (3.16%) T-muurolol(0.86%)
from dffi r ent comm,ercialsoa.rces.J. E ssent. Oil Re"s.,8, 38 I -290 y-cadinenet(4.8o%)
(1996 ). B-eudesmol(0.25%)
6-cadinene(12.97%) (1.610/0)
cx-cadinol
P. N. Kaul, B. R. RajeswaraRao, K. Singh and C. p. Singh,Effect of selinatriene*t(S.10%) (0.15%)
epi-o-bisabolol
paftial shafu on essential oils of thiee geranium (pblargonnm elemolt+ B-vetivenet germacronet(4.96%)
species)cultioars. Indian Perfum.,4I(l), l-4 (1997a). (1.21%)
P. N. KauI, B. R. RajeswaraRao,A.K. Bhattacharya,G. R. Mallavarapu
* correct
and S. I. Ramesh, Change in chemical iom:position of ,oie- isomer not identilied
t tentative identification
sce,nted geranium(Pelargoniumsp.)oil duringstorage.]. Essent. ** incorrect
identificationbased on elution order
O il Res..9.I15 -ll7 t1997b) .
AIso in 1995, Ferracini et al. analyzedthe composition of
B. R. Rajeswara Rao and A. K. Bhattacharya,Yield and chemjcal
cofitposition of the essential oil of rose-scented geraniurn oils produced from the leavesand flowers of female and male
(P-elargoniumspecies) grown in the presenceor absenci of ueeds. shrubs of B. dracunculfolia using GC and GC/MS. Their
FIav. Fragr. 1., 12, 20I-204 (1997). analytical data is summarized in Table X.
W. A. Kdnig, C. Fricke, Y. Saritas,B. Momeni and G. Hohenfeld, In 1996,Weyerstahlet al. used a combination of modern
Aduheration or natural aariabtllty? Enantioselectiae gas analytical techniques to determine the composition of a
chromatographg in purity control of eisential oils.J. High Reiol. commercial sample of vassouraproduced in porto Alegre,
Chromatogr.,20, 55-61 (1997).
Brazil from B. dracunculfolla. The authors initially sepa-
M. Wiirst, A. Rexroth, T. Beck and A. Mosandl, Struchre elucidation
rated the oil into an acidic fraction and a neutral fraction
of cis- and trans-rose oxide ketone and its enantiomeric analqsis
in geranium oils. FIav. Fragr. J., 12, 3Sf-386 (f997). using NaOH. The neutral fraction wasfurther separatedinto
V. K. Srivastava,B. M. Singh, K. S. Negi, K. C. Pant and p. Suneja,
Gas chromatographic examination of some aromatic plants of
Uttar Pradeshhills. Indian Perfum., 4f (4), 129-139(1997).
Table X. Percentage composition of oils
G. R. Mailavarapu,B. R. RajeswaraRao,P. N. Kaul and S. Ramesh, produced from female and male taxa of
Contribution of the essential oils of leof, petiole and stem of Baccharis dracu nc ul ifolia
scented geranium t o the od o u r of geri n i u m oi1.1. M edlcin. Arom.
Plant Sci., r9, 1020-1023(1997).
Compound Femaleoil Maleoil
P. M. Verin, P. Raharivelomanana,J-P. Bianchini and A. Cambon,
Etude de lafraction ester d'huile"essentielle.Rivista Ital. EppOS o-thujene 0.07 0.23
(Numero Speciale),591-595 (1998). s-prnene 1.18 0.13
B. M. Lawrence, unpublished information. B-pinene 3.76 1.90
cx{erpinene 0.14
VassouraOil limonene 4.65 0.93
terpinolene 0.40
In 1995,Loayzaet al.examinedthe chemicalcompositionof c)(,-terpineol 1.42 2.54
the oils ofthre eBaccharis speciesincludin gB. dracunculifolia, o-copaene 0.33 0.22
which is known commerciallyasvassouraoil. In the study,the
B-elemene | .zJ 1. 1 4
oil of B. dracunculifuliawasproduced from plants collected o(-gurlunene 0.45 0.28
in the high valleys of Bolivia in the province of Cochabamba. B-caryophyllene 5.40 5.90
The oil, which was analyzed bv GC (retention indices and aromadendrene t.oJ 1.06
quantitative data on both polarand non-polar columns) and o-humulene 1.55 2.25
GC/MS (peak identity confirmation), was found to contain: allo-aromadendrene o.92 0.83
B-selinene 9.90 1 1 . 00
othujene (0.50%) terpinen-4-ol (0.22%) B-cadinene.. 1.20 0.09
o-pinene(3.23%) o-terpineol(0.09%)
cI-muurotene 0.90 0.48
B-pinene(17"23%) cr-cubebene (0.51%)
sabinene(0.69%) 6-cadinene 5.07 3.58
o(-copaene(1.07Y")
myrcene(1.52%) (E)-nerolidol 20.80 1 2 . 02
B-elemene (0.16%)
crterpinene(0.15%) spathulenol 2.58 3.79
o,-gurjunene (0.31%)
p-cymene(0.26%) B-caryophyllen€ (3.23o/") globulol 2.46 2.26
limonene(4.17o/o) B-bourbonenef(0.30%) viridiflorol 1.34 1.12
B-phellandrene (0.82./") aromadendrene (0. 5%) guaiol 0.86 0.83
(E)-B-ocimene (0.46%) guaia-6,9-diene (0.36%) cr-cadinol 2.50 3.01
T-terpinene(0.41%) 0,-humulend'(0.68%)
terpinolene (O.67%) aromadendrendiol 1.86
allo-aromadendrene (1.10%)
linalool(0.12%) y-gurjunener(0.98%) ** incorrect
identification
basedon elutionorder
oln
a polar sub-fraction and a non-polar sub-fraction using 3-methylbutyl3- cubenol(0.3%)
liquid-liquid partition with MeOH/HrO (1:10) and hexane. phenylpropionate (0.4%) o-cadinol(1.6%)
5,11-epoxycadin-1 (10)-ene+ opposita-4(1 4).11(12)-dien-
Further fractionation ofthe polar sub-fractionwas achieved
1 0 - e p i - j u n e n(o1l . 8 %) 1 B - o l ( 0 . 1 %)
by vacuum fractionation and flash chromatography using globulol+ tran* germacra-4(1 5),5,10(14)trien-
silica gel columns or silica gel impregnated with AgNO.. dracunculifoliol + salvia- 1 B 'o l ( 0 . 3 %)
As a result of this exhaustivebut necessaryfractionation 4(15)-en-1 -onea( .4%) (E,E)-3,7,11-trimethyldodeca-
scheme,the oil was subjected to GC and GC/MS analysis. viridiflorol + B-oplopenone 1,6,9-trien-3,1 1-diol(0.6%)
(1.0o/o) 4-methyl-6-isopropyl-1 {etralone
The oil, which possessedmonoterpene hydrocarbons
ledol(0.7%) (0.1o/o)
(approximately 197), oxygenated monote lpenes (approxi- h u m u l e n eo x i d el l ( 0 . 1 %) (E)-5-hydroxynerolidol (0.2%)
mately2Va),sesquiterpene hydrocarbons(approximately38V) 4(1S)-dehydroglobulol (0.1o/o) (E,E)-isobicyclogermacra-1 (10),
and oxygenatedsesquiterpenes(approximately357o), was junenol(0.4%) 4-dien-5-al+ (Z)-3-hexenyl
found to contain: T-cadinol+ T-muurolol 3-phenylpropio nale (0.2Y")
( 1 . 3 %)
d,-thujene (0"1%) o(-copaene + methyleugenol
a also known as mint ketone
rx-pinene (2.9%) (0.7o/o)
sabinene(0.1%) ethyldecanoate(0.2%) I. Loayza, D. Abujder, R. Aranda, J. Jakupovic, G. Collin, H.
B-pinene(5.9%) B-elemene (1.6%)
Deslauriers and F-I. lean, Essential oils of Baccharis salicifulia,
myrcene(1.0%) B-damascone (<0.1%)
B.latifulia and B. dracuncuhfuIia.Phytochemistry,38, 38I-389
6-3-carene (0.1%) propyl3-phenylpropionate (0.7%) (1ee5).
c{erpinene(0.1%) B-caryophyl lene (6.2"/.)
p-cymene(0.1%) 2,2-dimethyl-6-vinylchromene + V. Ferracini, L. C. Paraiba,H. F. Leitao Filho, A. G. da Silva,L. R.
limonene(8.4%) y-elemene(0.4%) Nascimento and A. j. Marsaioli Essential oils of seoenBrazilian
acetophenone (0.2%) cabreuvaoxideA (0.3%) Baccharisspecies. J. Essent.Oil Res.,7,355-367(f995).
yterpinene(0.1%) aromadendrene (3.3%) P. Weyerstahl, C. Christiansen and H. Mosandl, Constituents of
terpinolene(0.2olo) a- hum ulene ( 1. 9% ) BrazilianYassoura oil. Flav. Fragr. J., 11, 15-23 (1996).
linalool(0.4%) cabreuvaoxideB (1.3%)
(Z)-4,8-di methylnona- cabreuvaoxideC (0.1%) Bois-de-rose oil
1,s,7-triene (0.1%) allo-aromadendrene (1.1%)
(E)-4,8-dimethylnona-1,3.7-(E)-B-ionone (0.07%) According to Ohashi et al. (1997),bois-de-roseoil or Brazil-
triene(0.4%) cabreuvaoxide D (0.4%) ian rosewoodoil was at one time the only sourceof racemic
p-methylacetophenone 1-muurolene (2.1%) linalool for the fragrance industry. For example, they
(<0.1 % ) isobutyl3-phenylpropionate + reported that in the early 1960sthe oil production and export
terpinen-4-ol+ p-cymen-B-ol sec.butyl3-phenylpropionate +
+ safranal(0"1%) 10,11-epoxycadina-4,9-diene
from South America was approximately500 tonnes. There
o-terpineol+ myrtenal(0.60lo) (0.2o/o) were approximately50 distilleries;Brazil was the dominant
myrtenol+ethyloctanoate germacreneD (3.6%) oil producer. By the mid-1980s, the volume of oil had
(0 .1% ) 10,11-epoxycalamenene (0.3%) dropped to approximately100 tonnes,which is also today's
trans-caNeol(<0.1%) cls-calamenene (1.0%)
volume. Becauseits price is higher than either sprthetic
cls-carveol+ citronellol+ bicyclogermacrene (3.1%)
n ero l(0 .1% ) ledene(3.6%)
linalool or ho wood oil and ho Ieaf oil, which are the source
cuminaldehyde + carvone+ cx-muurolene (0.9%) of L-linalool, it is only used in up-market top-of-the-line
neral+ (Z)-4,8- isohumbertiol A + isohumbediol C Iragrances.
d imethylnona-3,7- dien-2- ( 0. 1% ) In 1987, Gaydou and Randriamiharosoaused enantio-
one (0.1olo) T-cadinene (1.3%)
meric complexation with either (R)-(+)- or (S)-(-)-i-
geraniol(0.1%) 1,6-epoxyeudesm-4(1 5)-ene
geranial+ methyl3- (0.2%) phenylethyl isocyanate for the separation of linalool
phenylpropionaie + methyl 6-cadinene(5.6%) enantiomers.GC was nerformed on a 50 m x 0.30 mm fused
citronellate (0.1%) frans-calamenene (0.5%) silica capillary col.rmn coated with XE-60-s-valine-s-d,-
(E)-4,8-dimethylnona-3,7- isohumbertiol B + isohumbertiol D phenylethylamide.Using this technique, the authors were
dien-2-one(0.1%) (0.3%)
able to show that rosewood oil contained a racemic mixture
(E)-anethole + safrole pacifigorgiol (0.6%)
(<0.1 % ) o.-calacorene + cls-dracunculifoliol
of 3R(-)- and 35(+)-linalool. The authors speculatedthat
vitispirane A + vitispiraneB + exo-1,5-epoxysalvial-4(1 5)- the racemic mixture was probably formed during the
(<0.1 % ) ene (0.9%) hydrodlstillationof the oil. It is alsoequallypossiblethat the
(Z)-3-hexenyl tiglate(<0.1o/.) 4-epi-maaliol (0.2%) oil could have been adulterated with slnthetic racemic
theaspirane A (<0.1%) endo-1,5-expoxysalvial-4(1 5)-ene linalool.
theaspiraneB + methyl (0.1./.)
geranate(<0.1%) (E)-ner$idol(15.0ol.) Using multi-dimensional GC/MS and a Lipodex C chiral
ethyl3-phenylpropionate waitziacuminone (0.3%) column, Bernreuther and Schreier (1991) determined that
(0.1 % ) 10-epi-globulol(0.2'l") the enantiomeric ratio of linalool in a commercial samoleof
6-elemene(0.4%) alustrol(0.6%) Brazilian rosewoodoil was (R) - (-) linalool (50.2Ea), ( S)- ( + )-
nerylacetate(0.2%) maa,lbl(0.3%) linalool (49.8Eo).Furthermore, the authors were not con-
geranylacetaie(0.1%) spathulenol (3.5%)
(E)-B-damascenone + caryophylleneoxide (0.6%)
vinced that the existenceof racemiclinalool in a commercial
isopropyl3- 2-methylbutyl3-phenylpropionate oil was a true reflection of the enantiomeric distribution of
phenylpropionate (02%) (o.4%) linalool in an authentic samnle of rosewoodoi-.
248
Ohashi et al. (1997) examined the chemical com-
position of rosewood oil produced from wood and Table Xl. Comparative chemical composition (%)
leaves collected from Cuma Una in Southern para of bois-de-rose wood and leaf oils
(Brazil) and compared them to commercial samples
of rosewood oil. A summary of the resuits Compound Woodoils Commercial wood oils Leaf oils
b"
found in Table XI. In addition, the authors ""tr
found (Z)-B-ocimene-. 0.03-0.20 0.08-0.20 t-0.06
that the enantiomeric distribution of linalool B-pinene t-0.10 0.40-o.44 t-0.03
varied from leaf oil to wood oil and between trees in myrcene 0.04-0.06 t-0.50 0. 06- 0. 10
limonene 0.10-0.56 0.44-0.55 0. 10- 0. 15
the following way:
1,8-cineole I 0.44-0.80 0.03-0.04
leafoil: (3R)-(-)-linalool
(22.2./.): (3S)-(+)-tinatoot
(77.B%) (E)-B-ocimene 0.03-0.07 t-0.06 0.03-0.05
woodoil 1: (3R)-(-)-linalool
(10.0%): (3S)-(+)-tinatoot
(90.0%) p-cymene t-0.03 0.06-0.09 t-0.03
woodoil 2: (3R)-(-)-linalool
(65.5%): (3S)-(+)-tinatoot
(34.5%) cis-linalooloxide+ 1.00-1
.68 1.10-5.80 1. 20- 1. 80
E. M. Gaydou and R. P. Randriamiharosoa, Gas frans-linalool
oxide+ 0.90-1.60 1.10-5.20 1.00-1.54
chromatographic diastereom.erseparation of linalool cyclosativene t-0.90 0.10-0.13 1. 40- 2. 70
derioatioes. Application to the determinati-on of the campnor 0.03-0.09 t-0.08 t
enantiomeric purity of linalool in essential oils. linalool 87.00-92.00 72.00:83.00 73.00-78.00
J. Chromatogr..SSO.Szb-f8t (1987). terpinen-4-ol 0"10-0.26 0.20-0.28 0. 14- 0. 53
A. Bernreuther and P. Schreier, Multi-dimensional gas hotrienol 0.10-0.20 0.10-0.1
6 0.40-0.54
r h ro maf ogra p h 11
/ mass spcct ro rrlcf,1J: a p owerfu I loo! y-selinene 0.20-0.37 o.34-0.42 0. 10- 0. 50
for the diiect'chiral et'aluationofaima rompiunds i, eremophilene 0.30-0.90 0.60-1.70 4.50-6.00
plant tissues. lI. Linalool in essential oils and fiaits. linalooloxide.(pyranoid) 0.10-0.27 0.10-0.60 0. 13- 0. 25
Phltochem. Analysis,2, 167-f70 (1991). linalooloxide-(pyranoid) 0.09-0.22 0.10-0.42 0.04
S.T. Ohashi,L. dos S. Rosa,]. A. Santanaand C. L. Green, caryophylleneoxide 0.10-0.15 0.10-0.30 0.80-0"95
Brcnilian roseu;oodoil: sustainable production and oil spathulenol tt 0.15-1.00 0.35-0.62
qu alitg management. Perfum. Flav., 22(2), 1-5 ( I 997).
benzylbenzoate 0.25-0.59 0.30-0.33 0.62-0.79
" correctisomernot identified
t tentativeidentification
** incorrectcomponent
tdentity
t furanoidform (notgivenby authors)
t = trace(< 0.01%)
249
Progress in Essential Oils
fromPerfumer
Reprinted & Flavorist,
March/April
1999,Vol.24,No.2, P. 35
Lovage Oil
In 1980, Lu et al. used TLC to prove that ligustilide was the B-phellandrene (16.47%) phthalide
(E)-3-butylidene
major phthalide in lovage root. Nine years lateq Cu et al. limonene(9.06%) (0.41"/.)
(Z)-B-ocimene (5.09%) (20.91'/.)
ligustilide.
(1989)examinedthe chemicalcompositionof lovageroot oil
(12.84%)
citronellal (E)-3-butylidene-4,5-
and comparedit to extractsof a similar lot of lovageroot. The citronellylformate(1.34%) dihydrophthalide(0.66%)
results of this studv can be seen summarizedin Table I. B-cubebene(3.09%) (Z)-3-validene-3,4-
Using GC and'CCZl,lSand GC-FTIR, Cu et al. (1990) s-selinene(1.16010) (0.23%)
dihydrophthalide
determined that the headspaceof lovage root trapped on B-selinene(1.B2o/o)
X{D-4 and eluted with diethyl ether possessed the following
composition:
A year latet Stahl-Biskup and Wichtmann (1991) com-
toulene(1.46%) sabinene(0.75"/") pared the chemicalcompositionof lovageroot oils produced
furfural(0.51%) B-pinene(0.48'/.) from the roots of adult Iovage plants and seedlings.The
a-pine ne(0.1 5% ) myrcene(0.18%)
camphene(0.31%) o-phellandrene(0.43o/o) results of thls GC analysisare found in Table IL
Methylene
oil Ethanol Freon Methylfuran Benzene chloride CyclohexaneHexane
(x-prnene 0.65 I.O I 2.67 0.69 0.69 0.18 1-49 0.60
camphene 0.07 1. 4 8 0.12 0.36 0.10 0.24 0.32 0.42
sabinene v.ta 1. 7 0 0.09 0.02 0.49 0.09 0.52 0.73
B-pinene 2.05 4.32 2.31 |.zc 1.23 1.08 2j 6 3. 28
myrcene 0. 45 0. 85 0.39 0.03 0.20 0.53 0.39 0.48
o,-phellandrene 0,24 0.36 0.41 1.69 1.91 0.18 7.09 0.91
p-cymene 0.86 1. 0 4 0.27 0.40 0.71 0.54 0.35 0.42
B-phellandrene 0. 07 0.57 0.62 0.12 0.23 0.11 1.33 0. 37
limonene 0. 18 1. 0 3 0.23 0.16 0.42 0.19 0.13 0 .1 5
(Z)-B-ocimene 0.22 0.08 0.16 o.17 0.21 0.09 0.09 0 .1 0
(E)-B-ocimene 0.63 0. 42 0.40 0.34 0.63 0.25 0.04 0.07
yierpinene o.74 0.57 0"73 0.07 0.87 0.45 0.25 0.38
tarninnlana 0.37 0. 1 7 0.11 0.13 0.18 0.39 0.06 0.09
pentylbenzene 0.47 0.55 0.58 0"32 o.29 0.25 0.68 0.60
pentylcyclohexane 0. 13 0.50 0.54 0.24 u. t5 0.38 0.14 0.24
cI-copaene 0. 19 0.24 0.39 0.15 t 0.15 0.29 0 .3 7
R-nr rhahano 0.87 0. 2 8 0.84 0.90 t z.z I 1.28 0 .9 6
y-DEilr rEr rc 1. 58 0. 1 4 0.13 0.08 2.02 0.07 0.13 0 .2 1
B-selinene 5.92 4.49 0.08 0.65 9.05 11 . 1 8 0.42 0.38
linalool 2.79 4.43 t - oz 1.06 1.05 0.36 3.05 2.57
o-terpineol 4.12 0.48 0.62 12.72 0.42 0-47 0.98 0.87
bornylacetate 0.26 0. 2 1 0.27 2.43 2.20 0.22 1.02 0 .9 9
u-terpinylacetate 0.P 3.79 1.28 0.87 t 0.63 0.67 0.54
(Z)-3-butylidene
phthalide 1. 9 8 1.78 1-87 1.08 z . tz 1.08 1 .0 9
3.24
phthalide
(E)-3-butylidene 1.33 0.90 1.45 0.59 0.89 2.57 2.61 3 .1 7
Ql Zg
3-butylidene-4,5-dihydrophthalidet 62.38 58.58 50.89 63.87 57.62 40.15 45.37
(E)-3-butylidene-4,5-dihydrophthalide
0.55 0.67 0.31 0.51 0.63 0.47 o.37 0.22
(Z)-3-validene-3,4-dihydrophthalide
0.39 0.32 0.28 0.33 0.35 0.26 0.18 0 .2 1
250
The following year, Szebeni-Galambosiet al. (1992) ex- In 1992, Perineau et al. showed that hydrodistillation of
amined the composition of lovage root oil produced from lovage oil using a system fitted with a cohobation unit
roots harvested 400-850 days after transplantation. Using generatedan oil richer in the aroma-characteristicphthalides
GC/MS asthe method of analysis,the authorsfound that the than if the oil was produced without cohobation. The in-
oils contained: creasein total phthalides was from 60-85Voover the same
rr-pinene(2.08-7.87o/o) (Z)-B-ocimene (0-0.48%) di sti l l ati ont i me peri od.
camphene (0.54-2.66"/") terpinolene (0-25.85%) The following year, Blank and Schieberle (1993) used
B-pinene (2.4B-B.680/0) pentylcyclohexa-1,3-diene CC-olf'actometry or Aroma Extract Dilution Analysis to
sabinene$-1.78%) (12.15-29.25%)
determine the compounds responsiblefor the tlpical sea-
myrcene (0.30-0.77'/") (Z)-3-butylidene phthalide
limonene(0.49- 1.82'/.) (o-6.06%) soning-likeflavor of lovage.After isolationof the aroma-rich
B-phellandrene (E)-3-butylidene phthalide acidic fraction of a commercial lovage extract, the authors
(0.74-15.460/") (1.8o-4.48%) characterizedfive odorantsthat havehigh sensoryrelevance.
(E)-B-ocimene (0-0.68%) (Z)-ligustilide (37.33-62.47
%) The identity and threshold in air of these odorants (along
t = t r a c e( < 0 . 0 1 % )
with odor description, where available) are as follows:
aceticacid(30-90ng/L)(sourish/pungent)
Table ll. Percentage composition 3-methylbutyric
acid(1-2 ng/L)(rancid/sweaty)
of the major components of lovage root oils 4-hydroxy-2,5-dimethyl-3(2H){uranone
(0.5-1.5 ng/t,
of seedlingsand adult plants 2-ethyl-4-hydroxy-5-methyl-3(2H)-funanonea
(0.1-0"2ng/L)
3-hydroxy-4,5-dimethyl-2(5H)Juranoneb
(0.01-0.02ng/L)
a also known as homofuraneo
Seedling Adult b also known as sololone
Compound root oil root oil
21. 6 11.9 The authors also identified a trace amount of (E)-B-
B-p he llan dre ne
other monoterpenehydrocarbons 9.6 26.3 damascenonein this same acidic fraction of lovageextract.
(E)-B{arnesene 13.3 t In 1995, Venskutonisobtained some lovageplants fiom an
germacrene B 39.7 0.5 erperimental gardenin Kaunas(Lithuania).After separating
othersesquiterpene hydrocarbons 5.5 0.3 the plants into fresh leaves, stems and roots, oils were
c-terpinylacetate - 0.2
pentacyclohexa-1 ,3-diene 0.3 10.8 Table lV. Percentage composition from
(Z)-ligustilide 0.9 44.5
dynamic headspace analysis of various parts
of the above-ground lovage plant
t = t r a c e( < 0 . 1 % )
Flower Seeds Leaves Stems
Tablelll. Comparative chemicalcomposition(%) butanal 0.45 o' 0 .2 9
of oils producedfromvariousplantparts 2-methyl-2-propenal 0.22 :' u : t
ol Levisticumofficinale 2-methylbutanal I -I t
3-methylbutanal I -I t
Fresh Dried Fresh Dried Fresh pentanal I -I t
Compound leaf oil leaf oil root oil root oil stem oil cr-pinene 1.20 1.90 0.7 0 2. 00
ct-prnene 0.53 1. 37 0. 49 2. 17 2.60 o,-thujene 0.08 0.24 0.2 0 0. 14
sabinene 0.48 0.42 0. 14 1.47 camphene 0.22 0.75 0.27 0.53
B-pinene 0. 10 0. 18 0. 78 3. 36 1.22 B-pinene 0.26 0.90 0.37 0.45
sabinene 0.73 1.10 1.7 0 1. 90
myrcene 1. 82 4.59 0.43 0. 27 1.55
Iimonene 3. 01 - 2.91 o(-phellandrene 3.14 11.91 2.37 0-92
p-phellandrene 15.02 19. 95 0. 53 2.46 11.42 myrcene 4.30 4.20 3.30 2-00
d,-terpinene 0.70 4.80 0.80 0.29
pentylbenzene - t.10
limonene 5.60 2.60 3.00 3.60
pentylcyclohexadiene 0.40 0.53 2.68 19. 12 0.47
B-phellandrene 36.30 20.90 38.30 18.20
crterpineol 2.24 0. 41 _ 2.78
(Z)-B-ocimene 0.60 1.70 1.20 0 .9 3
0-terpinylacetate 43.39 47.30 - 45.02 yterpinene 1.40 2.11 2.60 0 .2 8
(Z)-3-propylidene (E)-B-ocimene 0.55 0.98 t t
phthalide - 0.85 p-cymene 2.33 3.50 7.11 0 .9 0
3-butylphthalide - - 1. 48 1. 19 terpinolene 1.50 0.86 t 0.45
(Z)-3-butylidene pentylcyclohexadiene* 0.56 1.66 r 0 .0 7
phthalide 0. 19 * 3. 08 z- t3
allo-ocimene* 0.40 t 0.32 0 .1 7
sedaneolide - 8. 10 o. to pentylbenzene 0.48 0.26 0.30 0.64
sedanolide - '' g. g8 6.93 bornylacetate 0.42 0.70 0.38 0.48
(Z)-ligustilide 15.47 54.51 44.26 13.46 a-terpinylacetate 4.70 0.80 2.60 6 .1 6
(E)-ligustilide 2.65 0. 52 1. 94 1. 72 0.97 - correclisomernot identified;t = trace (< 0.01%)
zDl
obtained from dried leavesand dried roots. These oils were Also in 1998, Bylaite et al. compared the composition of
subjected to analysisby GC and GC/MS and the results of oils produced from lovage stems and leaves at different
this study can be seen in Table III. stagesof developmentusing GC/MS. The authorsalsodeter-
In 1996, Bylaite et al, used dynamic headspacegaschro- mined the compositionof lovageflower oil and seedoil. The
matographicanalysisto compare the compositionof various results ofthese analysescan be seen in TablesV-VII.
plant parts of lovage.The resultsof the GC/MS analysesare
R-M. Lu, L-Y. He, H-J. Fang and X-Q. Zhang, Thin layer
shown in Table IV chromatographyand densometryof ligustllldein Umbellifurae
In 1998, Seidler-Lizykowskaand Kamiereczakexamined plants.ActaPharm.Sinica.,15,373-374(1980).
the oil content of2-year-old lovage plants at different stages
I-Q. C", F. Perineau,M. D elmasandA. Caset,Extraction of uolatile
of maturity. The authors found that the seedshad the highest corytounds ofloaageroot,celeryseedandcarrotseedbydffirent
oil content. They alsofound that the best time for harvesting solaents.In: Proceedingsof 11th International Congressof
lovagewas at lull flowering. Essential OiIs,Fragrancesand Flauors,New Delhi, Noo. I 989,
Table V. Percentage composition of lovage leaf oil produced from plants harvested at different stages of maturity
Stages of Growth
Young Mature 2nd set of
vegetative vegetative Bud Flowering End of See shoots
Compound Shoots growth growth formation grownpra
commencement flowering formation (newry
cx{h uje ne tttttttt
o-pinene O.37 0.58 0.46 0.58 0.70 0.60 0.62 0.77
ca mph en e 0. 10 0. 17 t 0.15 0.15 0.14 0"13 0 .1 6
sa bin en e 0. 52 0. 69 0.56 0.78 O.B2 1.07 1.01 1 .O4
p-p ine ne t 0. 12 t 0.12 0.17 0.14 0"15 0 .2 0
dehydro-1 ,8-cineole t t t t t t t t
myrcene 1.60 1.94 1.81 2.79 3.43 4.44 3.98 3.95
octan altttttttt
cr-phellandrene 0.48 0.53 0.45 0.45 0.95 0.68 0.72 0.72
crte rpin en ettttttt t
p-cyme ne t 0. 13 0.18 O.17 0.27 0.33 0.36 0 .1 7
p-phellandrene 13.43 17.90 14.39 17.53 20.08 20.52 21.37 21.15
limonene 2.35 2.46 1.90 2.O7 4.65 2.27 2.22 2.05
(Z)-B-o cime ne 0. 62 1. ' t 4 0.77 0.49 1.64 0.18 0"98 1 .0 1
(E)-B-ocimen ett t t O . 2lt t t
y-terpinene 0.23 0.37 0.52 0.39 1.20 1.56 1.58 1.57
terpinolene 0.34 0.40 0.26 O.25 1.58 0.37 0.36 0.25
lina loo l tttttttt
pentylcyclohexadiene 0.27 0.54 0.46 O.52 0.95 0.83 0.50 0.54
4-isopropylcyclohex-2-en-1-one t t t t t t t t
terpinen-4-ol t t 0.11 t t t t t
ote rpin eo l 1. 01 1. 50 1.12 1.04 1.02 0.69 0.88 0 .BB
ca rvo ne tttttttt
ge ran iol O . 12 0. 12 0.18 0.16 0.13 Oj2 0.14 0 .1 1
bo rnyla ce tate O . 17 0. 19 0.12 0.15 0.14 0.13 0.11 0 .1 3
crs-dihydro-uterpinyl
acetate t t t t t t t t
o-terpinylacetate 70.00 59.74 65.10 60.42 49.70 51.67 53.70 53.72
^^'^^"'
gsr ar ryr auErols 0.83 0.67 0.54 0.39 0.45 0.41 0.46 0.69
germacrene D 0.39 0.26 0.30 0.25 0.35 0.47 0.44 0.54
germamcreneA t t t t t t t t
germacreneB t 4* t t t t t t t
(Z)-3-b utylide pneht halide I O . 12 0.14 0.22 0.19 0.21 0.16 0 .1 9
ph
(E)-3 -bu tylid en e t halide A: 14 0. 18 0.18 0-17 0.10 0.16 0.11 0 .1 0
(Z)-ligustilide 414 7.60 7.51 7.85 6.49 11.70 8.39 9.73
(E)-lig ustilide 0. 36 0. 39 0.23 0.16 0.14 0.26 0.21 0 .1 7
t = trace (<0.1%);
252
Edits. S.C. Bhattachary,ya,_N.
Senand K. L. Sethi,Vol.4,pp. g9- F. Perineau, L. Ganou and C. Vilarem, Studging production of
97, Oxford and IBBT PirUt.Co., New Delhi (1989). loxage essential oils in a hydrodistillation pllol unit equipped
J-Q. C", F. Pu, Y. Shi, F. Perineau,M. Delmas and A. (]aset, The ruith a cohobationsystem.J. Chem. Tech. Biotechnol.,53,'iO5-
chemical composition of loaage Lrcadspaceand, e,ssential oils 171(1992).
pro&tced by soloent extraction u;ith oarious solnents.f. Essent. E. Blank and P. Schieberle, Analysis of the seasoning-like
Oil. Res.,2,53-59 (1990). Jlaaor
sybslancggof a commercial louige extract (Leaistiim
fficinale
tr. Stahl-Bisl:up and E. M. Wichtmann ,Corrytosition ofthe essential Ibch.). FIav.Fragr.J., 8, 191-t0b (1993).
oik from roots of someApiaceaein relatio,nto the diaelopment in P. R. Venskutonis, Essentialoil composition of someherbs cultil)ated
their oil duct systems.FIav. Fragr. I., 6,249-255 (199f). in Lithuania. In: Flaaours, Fragrancis ond Essential Oils.
Zs. Szebeni-Galambosi, B. Galambosiand Y. Holm, Crouth, uield Proceedings of the 13th International Congress of Flavours,
and essentialoil of louagegroron in Finland. f . Essent. Oil ites., Fragrances and Essential Oils, Istanbul, Turkey, Oct. 19g5.
4.375-380fi992). Edit., K. H. C. Baser,Vol. 2, pp. 108-123,Anadolu Univ. press,
Eskishir, Turkey (1995).
Table Vl' Percentage composition of lovage stem oil produced from plants harvested
at different stages of maturity
ot Growth
Young Mature 2nd set of
vegetative vegetative Bud Flowering End of See shoots
Compound Shoots growth growth formation commencement flowering formation (newly grown plants)
crthujene tt I I I I I I
o-pinene 1. 25 1. 16 1.08 1.01 0.76 1. 1 3 '1.06 1 .1 5
campnene 0.43 0.38 0.29 0.31 0.23 U.JC 0.31 0 .3 1
sabinene 1. 21 0. 76 0.73 0.70 0.45 0.69 0.81 0.78
B-pinene 0.77 0.57 0.21 0.16 0.22 0.37 0.38 0.58
dehydro-1
,B-cineole 0. 17 r u. to I t I I I
ZDJ
PimentoOil
Table Vll. Comparative percentage composition
of lovage seed oil and lovage flower oil In 1993, Kollmannsbergerand Nitz analyzedlab-prepared
supercritical CO, extracts of Pimento dioica. Initially they
Lovage Lovage found that extracts made at 150 bar and 350 bar at 50oC
Compound seed oil llower oil possesseda tl,pical pimento-like aroma;however,at 350 bar
0-thujene t 0.11 when temperature was increasedto 70oC, off-aromaswere
(x-prnene 1. 47 1.01 detected. Kollmannsberger and Nitz analyzed the extracts
campnene 0.25 0.21 made under the three different sets of conditions even
sabinene 0.54 1.00 though the yield ofextract was greatestunder the 350 bar and
B-pinene 0.35 0.31
50'C conditions.They alsocomparedtheseanalyseswith the
dehydro-1 ,8-cineole t
myrcene 2. 19 7.12 analysisof a direct diethyl ether extract and a simultaneous
octanal 0. 21 0.17 distillation and extraction of pimento berries using diethyl
cx-phellandrene 1. 96 0.93 ether. The analyical procedure used was silica-gelchroma-
ct-terpinene I I tography,capillary GC using polar and non-polar columns,
p-cymene 0.59 0.92
and GC/MS. A summary of the analytical results obtained
B-phellandrene 61.50 40.82
limonene J. to 2.25 can be found in Table VIII. In addition, the authors charac-
(Z)-B-ocimene 0.54 2.50 terized a number of other constituentsthat were found in
(E)-B-ocimene 0.39 0.24 various extract fractions. Considered to be minor constitu-
y-terpinene 0.39 1.87 ents, these componentswere as follows:
terpinolene I 0.11
linalool 0 .1 1 o.22 camphene(3 ppm) cls-sabinenehydrate(2 ppm)
pentylcyclohexadiene 0.43 0.40 (Z)-B-ocimene (1 ppm) linalooloxide-furanoid(1 ppm)
4-isopropylcyclohex-2-en-
1-one 0"80 0.44 c-p-dimethylstyrene (1 ppm) B-phellandren-6-ol (11 ppm)
terpinen-4-ol t 0.14 8-elemene(1 ppm) f/'ans-piperitol (1 ppm)
c[terpineol t 0.31 o-cubebene(10 ppm) cls-piperitol(3 ppm)
methylsalicylate 0 .11 o-ylangene(6 ppm) hexanal(<1 ppm)
carvone 0 .1 0 0.27 o-copaene(35 ppm) benzaldehyde(<1 ppm)
phellandral 0 .1 0 0.15 B-cubebene (1 ppm) cinnamaldehyde (1-10 ppm)
bornylacetate 0 .1 3 0.14 cx-gurjunene (43 ppm) v a n i l l i n( 1 - 1 0p p m)
cls-dihydro-cr-terpinyl
acetate leA 0.79 cr-bulnesene (27 ppm) methylsalicylate(3 ppm)
or-terpinyl
acetate 4.56 16.27 aromadendrene (31 ppm) guaiacol(<1 ppm)
geranylacetate I selina-4,11-diene(35 ppm) 4-vinylguaiacolt (1 ppm)
methyleugenol o.20 0.10 y-muurolene (57 ppm) methylchavicol(6 ppm)
B{arnesene* 0.78 0.13 ar-curcumene (10 ppm) safrole(5 ppm)
germacreneD 0.82 1.00 zingiberene (25 ppm) (E)-isoeugenol (1 ppm)
germacreneA t t o-muurolene (a2 ppm) methyl(E)-isoeugenol (1 ppm)
germacreneB 0.47 0.37 germacrene A (11 ppm) 6-methyloxyeugenol (1-10 ppm)
(Z)-3-butylidenephthalide 0.69 0.51 B-bisabolene(4 ppm) palustrol(1 ppm)
(E)-3-butylidenephthalide 0.26 0.34 cis-calamenene (10 ppm) caryophyll-S-en-1 2-alf (1 ppm)
(Z)-ligustilide 1 4 .1 8 16.01 B-sesquiphellandrene isocaryophyllene oxide
(E)-ligustilide 0.23 0.27 (5 ppm) ( 1 - 1 0p p m )
cadina-4,1 1-diene(11 ppm) salvial-4(14)-en-1 -one (1 ppm)
* correctisomernot identified;t = trace (< 0. 1%)
cr-cadinene (11 ppm) globulolr(12 ppm)
cls-calacorene (3 ppm) humuleneoxide| (4 ppm)
lrans-calacorene (1 ppm) t e d o t t( j - 1 0 p p m )
E. Bylaite, A. Legger, J. P. Roozen and P. R. Venskutonis,Dynami,c camphor(1 ppm) e u d e s m o l(*1 - 1 0p p m )
headspacegas chromatography of fufferent botanical parts of ascaridole(3 ppm) s e t i n e n o t "( r1 _ 1 0p p m )
lorsage(Leaistia.rm fficinale Koch.). Spec. Publ. Royal Soc. carvone(11 ppm) e u d e s m o l(*1 - 1 0p p m )
Chem., 66-69(1996). geranial(<1 ppm) epi-cubenol (21 ppm)
linalylacetate(3 ppm) caryophylla-2(1 2),
K. Seidler-Lizykowskaand K. Kazmiereczak,Content ofthe essential
aceiate(10 ppm)
o,-terpinyl 6(13)-dien-S-ol (12 ppm)
oil in the plant organs ofloaage (Leoisticum fficinale lbch. ) and
nerylacetate(2 ppm) isospathulenol (7 ppm)
yield of the rau material in different stagesof its deoelopment. geranylacetate(6 ppm) (1-10ppm)
cubenolT
Herba Pol.,44(1),1r-i5 (1998).
trans-sabinene hydrate(2 ppm)
E. Bylaite, R. P. Venskutonisan dl.P .Roozen,Influence ofharoesting
* correct isomer
time on the composition o.f aolatile c-omponentsin dffirent not identified; f tentative identification
anatomic al p art s of loaage (Leoi,sticumffi cinale Y,och.) . i." Agnc.
Food Chem., 46,3735-3740 (1998)-
254
Table Vlll. Yield in ppm of component identified Table lX. Percentage composition of a
in each of the pimento extracts steam-distilledoil, a hydrodistilledoil and a
supercritical CO, extract of Mexican pimento
CO^Extracts
Steam-distilled Hydrodistilled Supercritical
Compound 150/50350/50 350t0 SDE Etherextract Compound oil oit CO, extract
s-pinene 40 60 39 50 46 o(-ptnene t 0.1 T
B-pinene 39 55 37 56 t 0.2
B-pinene i
myrcene 38 48 37 79 sabinene 0.3 0.3 0. 2
(E)-B-ocimene 23 29 23 48 myrcene 17.7 I o.J 6. 0
cr-thujene 23 31 21 31 27 6-3-carene I I
sabinene 24 36 24 26 t
o-terpinene I 0.1
6-3-carene 55 74 52 102 95 p-cymene 0.2 I t
o-phellandrene 107 138 101 1BB 138 limonene 0.7 I t
Iimonene+ 1,8-cineole 1.9 4.1 1. 3
B-phellandene 138 188 119 298 233 (Z)-B-ocimene t 1.2 0. 9
p -cymen e 85 111 79 193 171 y-terpinene '1.1 0.2 t
0 terp ine ne 16 19 13 38 11 terpinolene I 0.6 0. 4
y-terp ine ne 87 111 83 183 150 linalool 0.4 t t
terpinolene 145 199 136 261 170 terpinen-4-ol 0.3 0.5 0. 3
1,8-cineole 272 355 249 472 403 methylsalicylate I I
linalool 32 43 30 48 0. 4
d-terpineol 0.7 0.7
te rpin en -4-o l 110 160 107 198 123 eugenol 17.3 8.3 14,9
p-cymen-8-ol 21 31 22 41 20 methyleugenol 48.3 62.7 67.9
o-terpineol 47 70 47 90 44 6.2 2.7 5. 2
B-caryophyllene
lrans-p-menth-2-en- cr-humulene 1.1 o.2 0. 2
1-ol + cls-o- y-cadinene 0. 2
0.6 0.1
menth-2-en-1-ol 16 21 15 31 15 t t
B-selinene I
B-caryophyllene 1749 2534 1595 1915 1838 o-selinene 0.4 t t
s-humulene 423 610 380 452 414 6-cadinene I t I
cx-selinene 267 383 236 262 237
B-selinene 173 243 153 173 161 t = trace(< 0.1%)
8-cadinene 210 307 1BB 216 186
B-e leme ne 105 150 95 113 113
This sameyear,Pino et al. (1997) analyzeda leaf oil of P
allo-aromadendrene 81 118 73 83 82
germacreneD 82 121 77 43 77 d)oica of Cuban origin using GC/MS and retention inclices
spathulenol 42 54 39 47 34 on a non-polar capillary column. They found that the oil
caryophylleneoxide contained:
+ viridiflorol 187 225 147 168 142 cr-pinene(0.56%) a-humulene(10.12%)
humuleneoxidell 39 55 35 47 34 myrcene(0.19%) rene(2.13%)
allo-aromadend
T-cadinol+ cr-phellandrene (1.12%) (2.77%)
o-amorphene
T-muurolol 76 103 66 79 55 p-cymene(1.87%) cr-muurolene(1.760/")
cr-muurolol 29 38 25 29 21 1,8-cineole (14.50%) calamenene* + y-cadinene
o,-cadinol 60 90 56 78 51 l i m o n e n e( 0 . 1 0 %) (11.12%)
selin-11-en-4-ol 131 170 113 120 78 y-terpinene(0.56%) 6-cadinene(5.49'/.)
caryophylla-2(12), terpinolene (1.38%) (0.49%)
cadina-1,4-diene
6(7)-dien-5-ol 30 37 25 28 29 menthol(0.56%) s-calacorene(1.23%)
eugenol 18176 29976 18178 22240 11135 methylchavicol(0.09%) caryophyllene oxide(2.69%)
methyleugenol 1822 2670 1661 2025 1424 carvone(0.10%) s-eudesmol(0.52'/.)
chavicol 57 73 58 60 25 thymol(1.00o/.) B-eudesmol(0.82%)
myristicin 33 44 26 31 23 carvacrol(1.00%) T-cadinol(6.64%)
ele micin 13 19 12 15 10 eugenol(28.O4%) o,-cadinol(4.94%)
B-caryophyllene (1.00%)
zDit
calamenene*+ y-cadinene T-cadinol(0.17%)
(0.05%) o,-cadinol(O.37o/o) Table X. Comparative percentage composition of
caryophylleneoxide (0.07%) lime oil and a SFCO2extract fraction of the oil
" correct isomer not identified
Compound Lime oil SFCO^extract fraction
H. Kollmannsberger and S. Nitz, Uber die Aromastoffzu-
sammensetzung aon hoch-druck-extrakten:2 Piment (Pimentct 0,-sanlatene t o.o2
(I-thujene t 0.02
dioica). Chem. Mikrobiol. Technol. Lebensmitt., 15(3/4),116-
126 (1993). s-prnene 1.01 0.03
o-fenchene t 0.03
J. Garcia-Fajardo, M. Martinez-Sosa,M. Estarron-Espinosa,G. camphene 0.79 0.37
Vilarem, A. Gaset andJ. M. de Santos,Comparatioe studtl of tlrc
sabinene I 0.28
oil and utpercritical CO, ertract of Mexican pimento (Pimenta
B-pinene 1.69 0. 17
dioica Mercill). |. Essent.Oil Res.,9, 181-185(1997).
myrcene 1.38 0.34
J. A. Pino, J. Garcia and M. A. Maftinez, Solt:ent extraction ancl 6-2-carene 0.52 0. 57
supercritical car*on dioxirle extraction of Pirnentadioica Merrill 1,4-cineole 4.BB 3.36
Ieaf. J. Essent.Oil Res.,9, 689-691(1997). p-cymene 8.57 3-07
lrmonene 42.97 tJ.v/
(Z)-B-ocimene o.47 0.20
Lime Oil (E)-B-ocimene 0-22 0.08
In 1990, Edwards and Marr determined that a peel o-terpinylacetatet 0 .1 5
y-terpinene 8.73 2.46
oil extract of Citnts latfolia from Florida contained the
terpinolene 7.61 5.28
following: linalool 0.59 2.30
(0.03olo)
B-santalene (0.05%) cls-Bterpineol t.Jz 4.5 9
B-santalol
trans-B{erpineol 0.93 4.52
In comparison,a juice-oil extractfrom the samelimes was borneol 0.75 3.25
found to contain: terpinen-1-ol 1.04 5 .3 1
terpinen-4-ol 1.03 5.72
o-santalene(0.06%) (0.11%)
B-santalene p-cymen-8-ol 0.23 t
o-terpineol 8.44 27.66
In 1993, Chamblee and Clark reported that distilled llme
dihydrocarveol 1.24 2.8 0
oil and expressed lime oil contained: geranial t t
verbenone 0"6 0
C.o hydrocarbons alcohols(1.05%,13.41%)
nerol 0.12 0.5 2
(25.367"a,3.31%b) esters(0.44%,0.15%)
nerylacetate 0.1 7
C.u hydrocarbons ketonesand esters(0.04%,
(5.70%,3.48%) 3.96olo)
geranylacetate ; I
aldehydes(5.00%,0.48%)
Q ^t^-^^^
P-VrEr I rvr ru 0.21 0.1 3
cls-jasmone I t
Njoroge et al. (1996) analyzed a cold-pressed oil of B-caryophyllene o.92 1-46
Tahitian Iime (Citrus latifolia Tanaka) using both GC and
lrans-c)[-bergamolene 1.17 1 .9 1
aromadendrene 0.14 0.1 8
CCiMS. The components identified u'ere as follows:
epi-B-santalene 0.10 0.35
othujene (t) pentadecane(t) Y-gurlunene 0.22 0.45
(3.2ol.)
cx,-pinene decanal(0.1%) B-chamigrene 0.06 0.40
camp he ne(0 .1% ) borneol(t) y-muurolene 0.17 o.26
B-pinene(13.0%) linalool(0.2%) B-selinene 1.93 J. t3
o{erpinene(0.3%) nonylacetate(0.1%)
basedon elutionorder;t = trace (< 0.01%)
t incorreclidentification
limonene(52.2%) bornylacetate(t)
B-phellandrene (t) 0-bergamotene- (0.8%)
(Z)-B-ocimene (t) B-elemene (0.1%) germacrene D (0.1%) geranjol(t)
y-terpinene (17.0%) B-caryophyllene (0.3%) nerylacetate(1.4%) p-mentha-1,8-dien-1O-ylacetate
(E)-B-ocimene (t) undecanal(t) B-bisabolene(0.8%) (t)
p-cymene(0.1%) y-elemene(t) geranial(2.3%) perillylacetate(t)
terpinolene (0.7%) trans-p-mentha-2,8-dien-1-ol (t) (E,E)-cr{arnese ne (0.2%) r ^ +v^ i ^ ^ ^ ^ ^ l
r9Lr dugudr rdr
/+\
\t,,
octanal(t) B-santalgge(t) geranylacetate(1.0%) (E)-2-dodecenol (t)
nonanal(t) citronellylacetate(t) (E)-cr-bisabolene (t) (E)-nerolidol (t)
o-cubebene(t) (E)-B4arnesene (0.1%) B-sesquiphellandrene (t) (t)
viridiflorol
lrans-sabinenehydrate o,-humulene (t) perillaldehyde(t) spathulenol (t)
(0.1o/4 neral'(1.2%) tridecanal(t) hexadecanal (0.1%)
8-elemene(0.1%) o-terpineol (0.4%) germacrene B (0.1%) thymol(t)
(0"1%)
citronellal geranylformate(t) isopiperiienone (t) y-eudesmol(t)
zco
Table Xl. percentage composition of the votatile
portion
of cold-pressed persia-nlime bil anJ-ktii;;
oirs rype A and B
Compound 1 2 3 Compound 1
nonane 0.002 0 .0 1 4 0.017 dodecane
tricyclene 0.006 0 .0 1 1 0.013 0.006 0.034
0.012 decanal
o{hujene 0.560 0.391 0.075 0.211 0. 137
0.391 nerol
c[-ptnene 2.099 2.454 2.442 0.114 0.036 0.095
campnene neral .1.155
0.062 0 .1 1 7 0.113
I.JJ/ 1.148
thuja-2,4(10)-diene geraniol 0.052
t 0.005 0.005 0.049 0.037
sabinene+ B-pinene piperitone
12.931 23.360 24.327
T l+
6-methyl-5-hepten-2-one geranial+ perillaldehyde
0.017 0.013 1.861 1. 967
myrcene bornyl acetate 0.006
1-436 1_.264 1.179 0.008 0. 019
dehydro-1,8-cineole tridecane 0.003
t I
0.023 0. 013
oecane undecanal 0.013
I I
0.031 0.021
octanal 5-elemene 0.067
0.050 0.058 0.042 0.307 0.068
o-phellandrene nerytacetate 0.999
0 .0 1 8 0.033 0.027 0.077 0.079
3-3-carene geranytacetate 0.238
0.007 0.005 I
0.244 0.254
0-terpinene 0.270 B-elemene 0.069 0.178 0. 160
u .2 5 5 0.091 dodecanal
p-cymene 0.331 0.038 0.115 0. 079
0.323 1.947 crs-o-bergamotene
limonene 56.653 49.352 0.072 0.089 0.089
49.380 B-caryophyllene
(Z)-B-ocimene 0.057 u.c/c 1.068 0.977
0 .13 9 0.128 Irans-0-bergamotene
(E)-B-ocimene 0 .1 1 5 0.388 1.109 1.361 1. 353
0.343 (Z)-B{arnesene
y-terpinene 1 3 .5 4 1 0.008 0.012 0. 013
7.795 6.192 cr-humulene
c/s-sabinenehydrate 0.038 0.040 0.052 0.122 0. 112
0.014 (E)-B{arnesene
terpinolene 0.593 0.424 0.104 0.130 0. 120
0.306 B-santalene
lrans-sabinenehydrate 0.047 0.037 0.041 0.049 0.050
0.015 germacreneD
linalool 0 .1 8 4 0 .1 7 1 0.093 0.352 0. 159
0.170 s-selinene
nonanal 0 .0 1 1 0.022 0.043 0.110 0. 077
o.024 (Z)-cr-bisabolene
B{enchol I 0.009 0.122 0.153 0. 153
t (E,E)-o{arnesene+
crs-p-menth-2-en-1-ol 0.007 0 .0 1 5 0.015 B-bisabolene
frans-pinocarveol 0.008 0 .0 1 3 1.884 3" 180 3.0B0
t germacreneB
rrans-p-menth-2-en-1_ol I 0.007 0.142 o.497 0.335
0.054 tetradecanal
citronellal 0.039 0 .0 1 0 0.028 0.054 0.050
0.029 2,3-dimethyt-3-(4-methyt_3_
borneol 0.020 0.o27 0.018 pentenyl)-2-norbornanol0.053
isopinocamphone 0.003 0.017 0.067 o.071
o.024 campherenol
terpinen-4-ol 0.083 0.522 0.061 0.065 0.073
0.143 o-bisabolol
s-terpineol 0.280 0.281 0.079 0.091 0.096
0.213 hexadecanal 0.082 0.057 o.045
t = trace (< 0.001%); 1 = persian lim o,,
,"u"
zDt
Table Xlll. Percentagecomposition of distilled lime oils of differentorigins
Compound Peru lvory Coast Mexico Compound Peru lvory Coast Mexico
nonane 0.03 0.02 0.02-0.04 decanal 0.11 0.27 0.02-0.20
tricyclene 0.03 0,02 0.02 nerol 0.02 0.02 t-0.01
o-thujene 0 .0 1 t 0 .0 1 -0.20 neral 0.03 0.01 t-0.01
o(-prnene 0 .9 9 1 ,2 6 0 .9 4 -1.17 carvone t t t-0.02
cr{enchene 0.79 0.68 0.69-0.73 p-menth-1-en-8-yl vinylether t-0.01
2,6,6trimelhyl-2-ethenyl- piperitone t - 0-t
tetra-hydropyran O.24 0.18 0 .2 1 -0.24 geraniol 0.01 t 0.01-0.04
sabinene t t I geranial 0.02 0.04 0.03-0.04
B-pinene 0.77 1.90 1. 19 - 1 . 8 5 perillaldehyde 0.05 0.02 0.01-0.04
6-methyl-5-hepten-2-one 0.01 t t-0.01 decanol t t 0.01-0.04
myrcen e 1. 00 1. 17 0. 85 - 1 . 1 0 a-terpinen-7-al 0.02 0.01 t-0.01
2,3-dehydro-1,B-cineole 0.21 0.27 0. 19 - 0 . 2 9 bornylacetate 0.02 0.01 t-0.03
octanal 0.05 0.03 0.02-0.05 lrans-pinocarvyl acetate 0.01 0.01 t-0.04
cr-phellandrene 0.44 0.48 0.34-0.45 tridecane t 0.01 t-0.02
6-3-carene 0.03 t t-0.03 undecanal 0.01 0.02 0.01-0.06
1,4-cineole 3.52 3.72 2.43-3.22 b-elemene 0.05 0.04 0.05-0.08
o(-terpinene 2.35 1.47 1. 62 - 2 . 1 5 citronellyl acetate t 0.01 f0.01
p-cymene 2.30 2.17 't.81-4.28 nerylacetate 0.06 0.04 0.02-0.07
2,2-dimethyl-5-(1
-methyl-1- undecanol 0.01
propenyl)-tetrahydrofuran 0.02 0.03 0.30-0.36 geranylacetate 0-07 0.10 0"06-0.13
lim o ne ne 39. 19 38.95 40.49-42.24 B-elemene 0.06 0.04 0.05-0.08
1,8-cineole 4.35 9. 47 7. 15 - 7 . 4 5 isocaryophyllene t 0.09 t-0.07
(Z)-B-ocimene 0.20 0. 18 0"15 - 0 " 2 0 dodecanal 0.06 - t-0.01
2,2-dimethyl-5-(1
-methyl-1- cls-cx-bergamotene 0.06 0.04 0.04-0.09
propenyl)-tetrahyd
rofuran 0. 25 0. 14 0.18-0.24 uecyr
A^ ^ r ,l
acerare
^ ^ ^ +^ +^ I -
(E)-B-ocimene 0.45 0.45 0.20-0.40 B-caryophyllen e 0.42 0.43 0.52-0.57
y-terpinene IJ.JC I t.t I 8 .5 1
-10.94 dihydrocaryophyllene oxide t-0.01
ocTanol 0.02 0.o2 0 .0 1 -0.02 y-elemene t t t
p-mentha-3,8-diene 0 .0 2 0 .0 1 0 .0 1 -0.02 frans-o,-bergamotene O.72 0.62 0.45-0.80
terpinolene 9.70 7.28 6 .9 1 -8.59 (Z)-B{arnesene 0.09 0.08 t-0.06
p-cymenene 0 .1 6 0 .0 8 0 .11- 0.15 o,-humulene 0.08 0.07 0 .1 1 - 0 .1 5
linalool 0 .16 0 .1 4 0.11-0.22 B-santalene 0.04 0.02 0.03-0.08
unoecane o.o2 0.02 0 .0 1 -0.03 dodecanol t t 0.01-0.04
nonanal 0 .0 1 0 .0 3 0 .0 1 -0.04 T-curcumene 0.11 0.09 0.07-0.09
p-mentha-1,3,8-triene It t-0.01 cis-B-guaiene 0.09 0.08 0.08-0.16
cr{enchol 0.82 0.71 0.66-0.73 1,1,3cr,7-tetramethyl-1 H-1o,2,
B{enchol 0 .0 1 t t-0.02 2,3a,4,5,6,7p-octahydro-
myrcenol 0 .0 1 t 0 .0 1 -0.08 cyclopropa-[a]naphthalene 0 . 1 8 0.15 0 .1 3 - 0 ,2 4
allo-ocimene" tt cr-selinene 0.09 0.07 0.06-0.15
cls-limoneneoxide tt 0 .0 1 -0.03 (Z)-cr-bisabolene 0.11 0.08 t- 0 .1 4
terpinen-1-ol 1 ,2 7 0 .9 7 0 .7 4 -1.11 (E,E)-cr{arnesene 2.07 1.99 1 .0 9 - 2 .4 7
trans-limoneneoxide tt 0.02-0.04 B-bisabolene
frans-pinenehydrate 0.03 0.02 r-0.01 (Z)-y-bisabolene 0.01 t 1
4,8-epoxy-p-menth-1-ene 0 .0 3 t 0.02-0.03 6-cadinene 0.08 0.04 0.03-0.08
allo-ocimene" tt I / F\-ry-hica hnlano 0.04 0.02 0.01-0.02
cis-B-terpineol 0.80 0.72 0.69-0.91 1,1,3cr,Ttetramethyl-1 H-1a,2,
(Z)-B-ocimenol 3,3o,4,5,6,7B-octahyd ro-
isopulegol 0.08 t cyclopropa-[a]naphthalene 0.19 0.15 0. 13- 0. 25
isoborneol 0.06 0.05 o.ro-o . rs s e l i n a - 3 , 71 ( 1) - d i e n e 0.10 0.07 0.03-0.17
(E)-B-ocimenol elemol t - t-0.04
isopinocamphone 0.05 0.02 0.04-0.06 germacrene B 0.05 0.01 0.04-0.08
frans-B-terpineol 0.20 0 .10 -0.1 5 caryophyllene alcohol 0.06 0.05 0.02-0.09
borneol 0.82 0.64 0.59-0.70 caryophylleneoxide 0.02 t 0. 01- 0. 05
prnocamphone 0.05 0 .0 1 -0.05 tetradecanal 0.04 0.03 0. 01- 0. 04
terpinen-4-ol 0 .7 1 0.88 0.56-0.92 T-eudesmol 0.06 0.05 0. 03- 0. 10
p-methylacetophenone a? t-0.02 cr-cadinol 0.03 0.02 0. 01- 0. 03
p-cymen-B-ol 0 .1 1 * 0. 18 0 .1 2 -0.28 campherenol 0.03 0.01 0. 01- 0. 05
s-terpineol 7.00 7.36 7.O3-8.O4 o-bisabolol 0.06 O.02 0. 01- 0. 03
1-terpineol 1 .2 4 . 1. 07 1" 11 -1.31 epi-a-bisabolol 0.06 0.02 0. 01- 0. 03
il
dihydrocarveol+
258
selina-3,7(1
1)-diene(0.050,"7 y-eudesmol (0.05%)
Table XlV. Percentageenantiomericdistribution of germacrene B (0.03%) T-cadinol+ T-muurolol(0.02'l.)
selectedmonoterpenesin various lime oils (E)-nerolidol
(0.01%) cr-cadinol(0.04%)
caryophyllenealcohol campherenol(0.04%)
CP CP CP (0.07%) o,-bisabolol(0.06%)
Key lime Key lime Pension Distilled tetradecanal(0.02%) selin-7(1
1)-en-a-ol(0.01%)
Type A Type B lime lime
Compound (4). (1) ( 11) (6) -correct isomer not identified:
a italicsindicatesmajor component in
mixed peaks
(+)-B-pinene J.+-O,C J.5 9. 1- 10. 3 3.2-4.O t = tr ac e ( < 0.01% )
(-)-B-pinene 89.7-90.9 96.0-96.8
Also in 1997, Della Porta et al. compared the GC/MS
(+)-sabinene 1 5. 1- 15. 2 15. 2 18.2-23.4 analysisof a dlstilled lime oil lr'ith thaf of a fractionated
(-)-sabinene B4.B-84.9 84.8 76. 6- 81. 8 supercriticalfluid CO, (SFCO2) extractof the samelime oil.
(+)-limonene 97.1-97.4 97.3 97.3-99.6 91.3-94.5 The resultsof this studyare shownin TableX. As can be seen
(-)-limonene 2. 6- 2- 9 2. 7 0.4-2.7 5.5,8.7 from these results, the oil has been partially deterpenified
(+)-linalool 28.5-29.8 29.4 30.7-45.6 50.0-50.2 using SFCOT. Also,the high molecularweight psoralensand
(-)-linalool 70.2-71.5 70.6 54.4-69.3 49.8-50.0 coumarins were not found in the SFCO' extract, whereas
(+)-terpinen-4-ol29.2-29.5 29.4 18,6-24.9 42.3-45.0 theywere present in the oil although the level foundwas not
(-)-terpinen-4-ol 70.5-70.8 70.6 75.1-81
.4 55.0-57.7 i denri fi ed.
14 . 5- 16. 0 17. 2 19.2-25.5 43.2-46.7 Dugo et al. (1997) compared the composition of cold-
84.0-85.5 82.8 74.5-80.8 53.3-56.8 pressedKey lime and Persianlime samplesusing GC, GC/
MS and HPLC. The results of the analysisof the volatile
- numberof samplesexamined
portion of the oils can be seenin Table XI. In support of the
differences seen between the two forms of Key lime and
B-pinene(1.34%) o-terpineol(7.90o/o) the Persian lime, the non-volatile portion of the oils was
myrcene+ dehydro-1, y-terpineol(1.21%) found to possesssome differen"", *hi"h are summarizedin
8-cineole(1.34./.)a decanal(0.20%) Table XII.
octanal(0.04%) frans-carveol(t) More recently, Dugo et al. (1998) compared the compo-
o-phellandrene(0.46o/0) citronellol(0.02o/")
6-3-carene (0.01%) neral(0.02k)
sition of distilled lime oils produced in Peru, Ivory Coastand
1,4-cineole(2.32%) carvone(0.01%) Mexico. The results of this studv are found in Table XIIL
o-terpinene (2.84%) geraniol(0.02%) This same year, Mondello ei al. (1gg8) examined the
p-cymene(1.89o/o) piperitone (0.01%) enantiomeric ratios of some of the monotemenes fbund in
limonene+ 1,8-cineole decanol+ geranial(0.09%) bofh col d-pressed and di sti l l edl i rneoi l s ol i ari o us or igins.
(46.86%) perillaldehyde(0.02./")
(Z)-B-ocimene (0.20%) The authors used multidirrensional (heart cuttine) GC-GC
sabinylacetate"(0.01%)
2,2-dimethyl-5 undecanal(0.03%) using a SE-52 capillary column as the pre-column and a
(1-methylpropenyl)- 6-elemene(0.06%) diethyl tert-butylsilyl-B-cyclodextrinchiral column to obtain
tetrahydrofuran + decanoicacid + nerylacetate the results that are presented in Table XIV.
(E)-B-ocimene (0.68%) (0.04o/o)
7-terpinene (11.02o/o) undecanol(0.03%) D. J.EdwardsandL M. M arr,Preaiou,sltl
octanol(0.02%) geranylacetate(0.10%)
unreport ed sesquit ery enes
of limeoil (CitruslatifuliaTanalra).
J.Essent.Oil Res.,2, 137-138
cis-linalool
oxide-(0.02%) B-elemene(trace) (1e90).
frans-linalooloxide+ dodecanal(0.08%)
terpinolene + unknown cls-cr-bergamotene (0.06%) T. S.ChambleeandB. C. Cla*, Lemonandlimecitruse,ssential ctils.
(8.43%) (0.60%) Analysis and organoleytticeaaluation.In: Bioactioeoolatile
B-caryophyllene
linalool+ undecane(0.19%) lrans-cr-bergamotene (0.70%) compounds from plants.Edits.,R. Teranishi,R. G. Butteryand
nonanal(0.03%) (Z)-B{arnesene(0.10%) H,. Sugisar,r.a.
pp. 88-102,ACS Synp. SeriesNo. 525,Amer.
a-fenchol(0.79%) o-humulene(0.09%) C hem.S oc..\V ashi ngton r [993;.
myrcenol(0.08%) B-santalene(0.04%) S.M. Njoroge,H. Ueda,H. Kusunose andM. Sawarntra,lapanese
trans-p-menth-2-en-1-ol dodecanol(0.04%) sourcitrusfntits Paft lY. Volatilecompounds of Naaoshii'hiand
(0.02%) selina-4,11-diene(0.13./") Tahittlimeessential oi1s.Flav.Fr.agr.J.. lf . 25-29(1996).
terpinen-1-ol (1.20%) cx,-muurolene (0.03%) T. S. Chamblee,R. L. Kareliiz,T. Radfordand B. C. Clark,
cls-p-menth-2-en-1 -ol (t) B-selinene (0.01%) Ident-ificationof sesquiterpenesin citrus essentiol oils by
frans-B-terpineol (0.81%) 6-selinene(0.20'/") cryoJocusingGC/FT-IR. Oil Res.,9,f27-132(1997).
J. trssent.
(Z)-B-ocimenol (0.09%) d-selinene+ (Z)-u-bisabolene
isoborneol (0.08%) (0.17%) ,4. T. S.ChambleeandB. C. Clark,Analysi,s and chernistryof distilled
(E)-B-ocimenol (0.06%) (E,E)-o-farnesene (0.68%) limeoil (Citnts aurantfolia Su;ingie).|. Essent.Oil itei., S,ZOZ-
cisB-terpineol(0.22o/o) 274(r9e7).
B-bisaboldne(1.04o/")
borneol+ nonanol(0.69%) (Z)-ybisabolen e (0.04%) G. DeilaPorta,E. Reverchon,D. ChouchiandD. Barth,X,lanclarin
terpinen-4-ol (0.97%) epi-o-seliriene+ 6-cadinene and line peeloil proce,ssingby
sttpercriticalCO, desorytion:
p-methylacetophenone + (0.05%) deteryenationandhighmolea.riarweigl.ttcompounl elini nntio rt.
p-cymen-8-ol (0.13%) (E)-y-bisabolene (0.01%) J. Essent.
Oil Res.,9,515-522 (f997).
259
260
U. Ravid, E. Putievsly and I. Katzir, Determination of the U. Ravid,
enantiomeric composition of u-tetpineol in essentialoils. Fiavor. _E. Putievslgr and I. Katzir, Stereochemical analysis of
born eol i n e ssent i al-o il s usi ng p ermeI h qlat ed B-cqclodex t ii n as L
Frag r.j.. 10 .28 [-284 r 1995) . chiral stationary phase.Flav.'Fragr. f f , f'Of-iSS (1996).
1-
T. Ozek, F. Demirci, K. H. C. Baserand G. Tiimen , Compositionof F. Tateo, M. Mariotti and M. Bononi, Essential oil comnosition ancl
the essential oil of Coridothynxus copitatus (L) Relchb. enantiom.ericdistribution of somerlnnoterpenoid compone ntsof
flt. from
Tur*ey.j. Essent.Oil Res.,7,909-312(1995). C-oridnthymus capitatus (L.) Reichenb.
fit. grown oi t lana iy
I(r.s(Creece).Rivista Sci. Aliment.. 25(i), fdS-I07 (1996).
26r
Progress in Essential Oils
& Flavorist,
f romPerfumer
Reprinted 1999,Vol.24, No.3, P. 47
May/June
the herb prior to distillation was reported to change the 0.25 4.95
B-caryophyllene
relative amountsofthe constituents.For example,the amounts neral 26.08 19.75
of neral and geranialwere decreased247o and 30%, respec- cr,-terpineol 0.82 1 .4 4
tively, while the citronellal content increased I9B7o. geranial 38.32 26.80
However, one should not give credence to these changes geranylacetate 3.28 1 .7 6
because the authors did not carefully control the origin of neryl acetate 3.99 1 .4 5
their nlant material. geraniol 8.13 4.23
nerol 1.34 0.64
TGse sameauthorsexaminedthe compositionalchanges
caryophylleneoxide 5.49 9.99
that take place when fresh oil was stored in either clear glass
t=trace(0.01%)
or aluminum containers at ambient room temperature
conditions (27"C) or in a re-
Table ll. Change in percentage composition of
frigerator for one year. The
main melissa oil constituentsduring storage
most remarkable changes
that took placeare shownin Fresh oil Stored oil
Table IL Compound Glass Aluminum Glass Aluminum Room Temperature Refrigerator
AIsoinI 995,Venskutonis 15.38 2.44 0.76 2.69 1 .9 9
et al. used a combination of ;Hieu" 14.56 29.82 30.29 28.85 30.91
modern analytical tech- geranial+ geraniol 18.08 48.69 54.73 51.00 49.90
nerylacetate 2.71 1.26 0.70 0.87 0.65
niquesincluding GC (reten-
tion indices) and GC/MS geiS'nyt
acetate 5.33 1 . 6 9 1 . 1 8 1 . 2 4 1. 96
B-caryophyllene 11.39 5.52 4.55 1.72 5.00
(component identity confir-
caryophyllene oxide |0.10 3.93 4.42 5.40 2.99
mation) to examine an oil of
262
cls-linalooloxide-furanoid methyleugenol(0.33%) citronellal
(55.84%) geraniol(1.54o/o)
(0.33%) B-bourbonene (1.10%) linalool(3.22%) methylheptenonet
frans-|inalooloxideJu ranoid B-cubebene (0.55%) neral(4.93%) neroF
(0.17o/o) isocaryophyllene (t) geranial(7.55%) B-caryophyllener
6-methyl-3,5-heptadien-2- o-cedrene(t) citronellol
(15.0%)
one (t) B-caryophyllen e (7.10%)
linalool(1.09o/.) B-gurjunene (0.16%) t quantitative data not given
cis-roseoxide (0.19%) o-cadinenet(t)
frans-roseoxide (0.42%) Usai et al. (1997) compared the composition of oils of
s-humulene(0.86%)
citronellal(2.79%) allo-aromadendrene (0.12%) cultivated M. officinalis ssp. fficinalls with oils of wild
terpinen-4-ol(0.40%) B-iononst(0.13%) collectionso{M. fficinalis ssp.altissimafrom Sardinia.The
methylsalicylate(0.15%) y-muurolene(t) analyseswere performed on lab-prepared oils using GC
methylchavicol(7.48%) germacreneD (0.92%) and GC/MS. The oil compositions are shown in Table IV
B-cyclocitral(0.10%) o,-muurolene (t)
ciironellol(0.40./") germacreneBr (0.14%)
Kciniget al. (1997) used enantioselectiveGC to examine
nerol (0.52%) ycadinene (0.47%) the enantiomeric ratio of citronellal in genuine melissaoil.
neral(10.00%) 6-cadinene(0.39%) They confirmed that the enantiomeric ratio of citronellal in
geraniol(O.45o/") elemicin(0.19%) genuine melissaoil was:
geranial(14.79%) (Z)-nerolidolt(0.1S%)
methylgeranate(0.28%) spathulenol(t) (+)-(3R)-citronellal
(98-99%)
: (-)-(3S)-cirron
e|at (1-2%)
eugenol(t) caryophylleneoxide (2352%)
oterpinyl acetate(0.24/.)
In contrast, the enantiomeric ratio inlaaa ci.tronella (JC) oil
cubenol(0.12%)
citronellylacetate(t) T-cadinol(0.62'/") and Eucalyptus citriodoro (EC) oil (common melissa oil
o,-cubebene(t) cr-cadinol(0.34'/.) adulterants)was found to be:
geranylacetate(0.59%) (Z,Z)1 arnesol (2.98o/o)
o-copaene(0.83%) JC:(+)-(3R)-citronellal
(90%): (-)-(3S)-citroneilat
(10%)
t correctisomer
EC:(+)-(3R)-citronellal
(50%): (-)-(3S)-citroneilat
(50%)
1 incorrect
notidentified; identj{ication
basedon elutionorder
t = trace(< 0.01%) Therefore, the authenticity of an oil as judged by the
This sameyear, Hener et al. (1995) discussedthe use of citronellal content can be determined by analyzingmelissa
enantioselective GC and GC/IRMS (isotope ratio mass oil on a 50 m x 0.25 mm heptakis (2,6-di-O-pentyl)-
spectrometry)in determiningthe genuinenessofmelissaoil. B-cyclodextrin(507oin OV-17o1dw) fused silica
They pointed out that the adulteration of melissa oil with column temperature programmed from 70o-200oC at
1"C/min. -apiliary
synthetic racemates of cis- and trans-rose oxide, citronellal
and citronellol was easilydetected.In addition, as (+)-(3R)- AIso in 1997, Holla et al. analyzedan oil of M. fficinolis
methyl citronellate is found enantiomerically pure, it could 'citra' which was produced from plants grown in the Nitra
alsobe used to determine the oil purity asit was not found as locality (Slovak Republic) using a combination of GC and
a constituent of citronella oil, a common melissaoil adulter- GC/MS. They found that the oil contained the following
ant. Furthermore, the author showed that because M. constituents:
fficinalis is a C, plant and oils of Cymbopogon species oc-pinene (0.15%) c i t r o n e l l a( 1
l 1 . 3 1 %)
(citronella and lemongrass)are Cn plants, the S13(Zo)values 2,5-diethyltetrahyd rofuran. cx-copaene (0.67'/.)
of citronellal, citronellol, B-caryophyllene, geraniol, geranyl (0.08%) B-bourbonene(0.06%)
acetate, neral and geranial were very different and easily hexenal*(0.05%) linalool(0.08%)
1,3,S-octatriene. (t) isopulegol 1- (0.07o/o)
differentiated. Finally, the authors reported their results of
B-pinene(0.14%) isopulegol 2- (0.06%)
the enantiomeric GC analysis for five oil constituents, a myrcene(0.12%) menthylacetate(0.27%)
summary of which can be seen in Table III. l i m o n e n e( 0 . 1 1 %) B-caryophyllene @.20%)
The following year,Bomme et al. (1996)examinedthe oil 1,8-cineole (0.14%) menthol(0.12%)
yeld, growth habits, leaf odor and oil tlpe of 101 different 3-octanone(0.12o/") cr-humulene (0.13%)
ocimene*(0.26%) neral(22.180/")
collections of M. fficinalis grown in an experimental
4-octen-3-one (0.18%) meihylgeranate(0.36%)
garden in southern Bavaria (Germany). They found that, 2,3-octanedione (t) geranial(33.60%)
although the oil content varied from 0.027oto 0.30% for 6-methyl-5-hepten-2-one T-muurolene(0.26%)
the full range of collections screened,only certain types were ( 0 . 3 1 %) o(-muurolene (0.14%)
found to possessgrowth habits,leaf odor and major compo- rose oxide '1.(0.12"/.) geranylacetate(5.89%)
rose oxide 2- (0.07o/o) caryophylleneoxide
nent composition acceptable for commercial cultivation.
3-octanol(0.12o/o) (8.35%)
As a result, plant propagation of ths*12 collections that linalooloxide- (0.24o/o) geranicacid (1.05%)
possessedthe highest commercial potential was initiated by menthone(0.60%) myristicacid (0.80%)
the authors. '1-octen-3-ol (O.25o/o) palmiticacid(1.01%)
q,-cubebene(0.26%) heptacosane(t)
As part of a gas chromatographic'survey of oils produced
isomenthone(0.42%)
in Uttar Pradesh(India), Srivastavaet al. (1997) analyzedan
oil ol M. fficinalis produced from plants grown at Bhowali. ' correct isomer not identilied
t = tr ac e ( < 0.01% )
The found that the main constituents of the oil were:
263
Van den Berg et al. (1997) analyzed oils produced
Table lll. Percentageenantiomeric purity of selected
from wild growing M. fficinalis ssp. altissima of various
chiral constituentsof melissa oil and citronellaloil
origins and compared them with oils produced from M.
Java CeYlon
fficinalis ssp.fficinalis using both GC (for quantitative
Melissa
Compound oil citronellaoil citronellaoil
data and retention indices on two columns of differing
(+)-(2R,4S)-crs-rose oxide 97.4 84.5 8O.7 polarity) and GC/MS (for component identity confirma-
(+)-(2S,4S)-frans-rose oxide 97.6 87.O B2.O tion). The results of this study are summarized in Table
(+)-(3R)-citronellal 97.7 90.4 82.4
83.8 82.3
V. It is of interest to note that the oil content of M.
(+)-(3R)-citronellol 90.2
(+)-(3R)-methyl citronellate >99.0 officinalis ssp. altissima varied from 0.08% to 0.38%
while that of M. fficinalis ssp. fficinalis varied
Table lV. Comparative percentage composition of from 0.027oto 0.207o. Examination of the quan-
Sardinian oils of Melissa ofticinalis subspecies titative data presented in Table Y reveals that
the neral and geranial content of M. officinalis
Compound M. otficinalis M. officinalis
ssp. a/tissima
ssp.altissima did not exceed0.57o,whereas oils
ssp. officinalis
(2 samples examined) (3 samples examined) oioduced from a cultivated German strain of
M. fficinatis ssp.fficinalis at different stages
(Z)-3-hexenol <0.01
benzaldehyde <0.01 of maturity contained much more neral and
6-methyl-5-hepten-2-one 0.07-0.11 geranial, with increased levels of citronellal rn
3-octanone 0.09-0.13 oil produced during and after flowering. As a
6-methyl-5-hepten-2-ol 0.05-0.09 result, it can be concluded that melissa oil
cls-anhydrolinalool oxidet <0.01
produced from M. officinalis ssp. altissimo carr
frans-anhydrolinalool oxidet <0.01
limonene 0.05-0.07 be readily differentiated from oil produced
(Z)-B-ocimene 0.12-0.15 0-0.62 from M. fficinalis ssp. fficinalds. Also, oil
(E)-B-ocimene 0.44-0.52 0-0.91 produced from mixed subspecieswould result
linalool 0.25-0.73 in a decreaseof oxygenatedmonoterpenes and
p u leg ol- 0. 15- 0. 18
a corresponding increase in sesquiterpene
citronellal 6.48 o-o.ge
neroloxide 0.75-1.13 hydrocarbons.
isopulegol 1.24-2-00 Also in 1997, Hose et al. examined the oil
safranal <0.01 composition of leavesof M. fficinalis obtained
8-terpineol <0.01 from different stem positions on a single plant
citronellol 0.08-0.09
and compared these to the oil composition of
citronellylpropionate 0-0.87
neror 1.85-2.37 <0.01-0.59 the whole plant. As can be seen in Table VI,
neral 28.14-28.76 there were dramatic differences in the oil com-
ge r a n i o l 1 .9 9 -2 .5 0 <o.o1-0.72 position between the leaf oils produced from
piperitone 2.30-3.60 the different stem positions. On examination of
geranial 40.62-41.11
their results, the authors concluded that the
methylgeranate 0.24-0.25 o.rr-o.ss
neryl acetate < 0 .0 1 0-0.78 composition of the leaf oil was dependent on
geranicacid the position of the leaves on the stem and not,
geranylacetate o.90-1 .27 0.94-3.84 as has been previously assumed,on the age of
cI-copaene 0.19-O.22 <0.01-3.32 the plant. To complicate this further, the authors
4
0 .13 -0 .1 <0 . 0 1 - 3 . 4 0
did find that there were also age-dependent
B-elemene 0 .1 2 -0 .1 7
methyleugenol 0 .1 8 -0 .2 0 changesin oil compositionthat tookplace within
B-caryophyllene 5.59-5.87 20.53-31 .36 the secretory structures on the leaf. They found
germacreneD 0 .0 9 -0 .1 2 1.40-2.53 that, although the sum of citronellal, neral and
o(,-bergamotene* 0 .0 8 -0 .1 2 <0 . 0 1 - 1 . 6 0 geranialremained approximatelyconstantasthe
o-humulene 0.34-0.40 1.78-2.90
leaf aged, neral and geranial were converted to
0-muurolene 2 .1 1 -2 .3 0 17.57-44.80
0 .1 7 2.21-2,46 citronellal. The varied oil compositionof melissa
B-bisabolene
y-cadinene 0.30-0.85 <0 . 0 1 - 5 . 7 0 is of distinct importance for the pharmaceutical
calamenene* 0.05-0.06 0.12-0.42 use (antispasmodicand sedativeproperties) of
6-cadinene 0.30-0;46 1.70-2.07 the plant because the biological activity of neral
elemene+ 0.11-6i 4 0.21-6.50
and geranial has been found to be greater than
caryophylleneoxide 0.M--0.57 3.35-7.93
cr-cubebene+ 0-9.48 that ofcitronellal [Reuter and Brandt (1985)and
o,-terpineolt 0-0.53 Soulimaniet al. (1991)1.
T-cadinol "f 0-0.74
or-cadinol 0-3-27
* correctisomernot identified;t furanoidform;* incorrectidentification
basedon elutionorder
264
Table v. Percentage composition ol Metissaofficinalis ssp. a/fisslrna oils
compared with oils ot M. officinalls ssp. officinalis
Compound 1 9 10
s-prnene 0.28 0.05 3.57 3.13 0.30 0.1B 1.59 I I
B-pinene 0.59 0.08 8.03 7.05 0.53 0.40 3.62 0.03 I
sabinene 0.86 0 .11 1 4 .6 8 14.01 0.91 u.J / 5./5 I I
myrcene 0.05 0.02 0.30 0.35 0.04 0.50 0.1B 0.05 0.09 t
limonene 0.04 t 0.62 0.59 0.05 0.04 0.27 I I I
(Z)-B-ocimene 0.83 o.74 0.39 0.36 0.44 0.89 0.70 0.21 0.64 neo
yterpinene t 0.01 0.40 0.35 0.06 0.01 0.12 i I I
(E)-B-ocimene 3.37 3 .1 6 1.4 3 1.13 1.02 4.24 1.69 2.34 5.83 3.46
1-octen-3-ol 0 .1 4 0 .1 9 t t 0.04 0.06 t t 1.01 0. 09
citronellal 0.20 0.03 t tt 0.o7 0.31 7.14 18.77 19.22
c[-copaene 1 .4 9 1 .6 4 0 .3 4 0.64 0.36 1.55 1.05 t 0.40 0.45
B-cubebene 0 .9 1 0 .9 3 0 .10 0.09 0.30 0.86 0.62 I 0.56 0.62
B-caryophyllene 2 1.1 2 19.66 7.27 10.23 12.66 21.44 21.66 13.61 10.94 19. 91
terpinen-4-ol 0.06 0.04 0.81 0.61 0.15 0.04 0.09 t tt
aromadendrene 0.48 0 .4 4 0 .1 9 0.08 2.56 0.39 1.59 I 0.15 0. 01
neral t ti tt tt 12.88 3.87 0.43
germacreneD +o.Jc 53.90 34.79 37.57 51.50 51.33 32.49 I z,zJ 19.94 26. 16
geranial t tt tt 0.03 t 26.49 6.24 1. 10
geranylacetate 0.46 o.29 t tt 0.40 2.49 2.04 tt
citronellol T t 0.08 0.04 t t 0.10 0.35 0.34 0.23
nerol I tt tt rt o.25 tt
geraniol t tt tt t 0.06 0.98 0.08 t
isocaryophyllene
oxide 0.48 0.07 0.30 0.30 0.24 0.09 0.47 I 0.40 0.40
caryophylleneoxide z,zJ 0 .3 3 1 .7 5 1.62 1.36 0.47 2.24 0.14 1.19 1. 90
germacra-1(10)
E,5E-dien-4-ol 0.75 0.36 0.30 0.03 4.19 0.41 0.32 4.45 8.06 9.60
T-muurolol 0 .1 6 0 .0 9 0 .1 0 0.02 0.14 0.10 r T 0.10 0. 30
T-cadinol 0.20 r 0.08 0.03 0.10 0.02 t t 0.24 0.23
cr-muurolol 0.07 0.04 0.05 0.02 0.14 0.05 r I 0.28 0.51
cr-cadinol 0.28 0 .0 9 0 .1 9 0.03 0.56 0.15 0.13 T 1.96 1. 54
Legend
M. officinalisssp. altissima samples,all at full flowering
1. ltalyA 2. ltalyB 3. GreeceA 4. GreeceB 5. SpainA 6. HungaryA
M. officinalis ssp. officinalis samples
7- Germany,beforeflowering 8. Germany,at full flowering 9. Germany,postflowering 10. Germany,postflowering
t = trace (< 0.01%)
\1. Reuter and W. Brandt, Relaxant effects on tracheal and ileal G. Charalambous,p. 833-847,ElsevierScienceB. V., Amsterdam
smoothmasclesof the guinea pig. Arzneimitt. Forsch., J5(lA), ( 1995).
408-414(1e85).
U. Hener, S.Faulhaber,P. KriesandA. Mosandl,Orzrheauthenticitu
R. Soulimani,J. Fleurentin, F. Mortier, R. Misslin, G. Derrieu and eaaluation of balm oil (Melissa offlcinalis L.). pharmazie, Sd,
]. M. Pelt, Neurotropic acti.on of the hydroalcoholic extract of 60-62(ree5).
Melissafficinalis inihe mnusa.PiantaMed.,5Z 105-109(1991i.
U. Bomme, T. Stahn, G. Hillenmeyer and R. Rinder, Eoaluation of
\\-. Schultze, W. A. Kcinig and R . Richter, Dffirentiation of original a collection of Melissa fficinalis for essential oil,
bmo n b alm oil (M eltssa ffi cin alis)fr om seaeral leman -tlie smi'ltln g flaaour anh
grouing character_.In : Proceedingslntem,ational Symposium on
oils by chirospecifi,cGC analysis of citronellal and isotope rati6 Breeding Researchon Medicinal-and Aromatic plinti. ndit. , p .
?rL(LSS
spectrornetry. Planta Med., 59 (Suppl.), ,{635 (1993). pf 33-36, Bundesanstalt fiir Ziichtungsforschung an
l-Tk,
-{.S.Shalaby,S.El-Gengaihi and M. Khattab,O ilof Melissaoficinalis Kulturpflanzen, Quedlinburg, Germany ( 1996).
L. as affectedbAstorageandherb dryln1. Essent.Oil nes., Z, V. K. Srivastava,B. M. Singh,K. S. Negr, K. C. pant and p. Suneja,
].
667-66e(19e5). Cas chromatog-raphic examination-of some aromatic plants" of
P. R. Venskutonis, A. Dapkevicius and N4.,Baranaushene, Flaaour Uttar Pradeshhills.Itdian Perfum., 4l(4), 129-139(1997).
composition of somelemnn-like aroma herbs from Lithuania. In: M. Usai, A. D. Atzei, V. Picci and A. Furesti, Essentialoil
Foodflauors: generation. analysis ttnd procbss inflaence. Edit., front
Sardinian Melissa fficinalis L. and Melissa rolrulna t[iil. In,
zo5
Table Vl. Comparative percentage composition of the leaf oil of
Melissa officinalis produced from leaves of different stem positions
Compound Wholeplantoil Basal leaf oil Middle leaf oil Top leaf oil
myrcene 0 .1 2 I I
limonene I
(Z)-B-ocimene 0 .1 3 o.25 I
(E)-B-ocimene 4.60 i... 2.61 2.17
3-octanone I t
p-cymene t
0.12 :^^
6-methyl-5-hepten-2-one 0.60 U.OJ
cis-rose oxide 0 .1 1 I
lrans-roseoxide I
(Z)-3-hexenol 0 .1 6
3-octanol 0 .1 1 I ,
1-octen-3-ol 0.6s 0.54 I
B-guaiene- I I
neral 1 0 .1 3 t 3.17 ti.tz
methylgeranate 0 .1 2 0.12 I
germacreneD 1 0 .4 6 i,, 21.63 19.98
c[-muurolene I t I
bicyclogermacrene t I
geranial 16.32 7.07 26.O7
(E,E)-cr{arnesene 0.37 :* 1.O4 0.43
geranylacetate 0.94 10.16
6-cadinene+ citronellol+ y-cadinene 5.60 1.00 1.05 0.43
cadina-1,4-diene t
nerol 1. 21 I o.28
s-cadinene I I t
geraniol 3.42 t 1.77
(2,E,E)-allo{arnesene I
isocaryophyllene
oxide T
caryophylleneoxide 0. 17 0.12 0
humuleneoxide* I
germacra-1(10)E,5E-dien-4-ol 2.28 2.47 7.45 4.89
T-cadinol 0 .1 1 o.22 I
o-muurolol I 0.27 t
.*
'
cx-cadinol 0.36 0.53 1.07
citronellic
acid I
geranicacid I
* correctisomernot identified
t = trace (< 0.1%)
266
Proceerl)ngsof 27th, lnternational Symposium on essential oils.
Yienna,l996. trdits. Ch. Franz,A. Math6 and G. Buchbauer,pp. 9HfRs R1 R2 R3
221-223,Allured Publ., Carol Stream,IL (1997) Dienevalepotriates
W. A. Konig, C. Fricke, Y. Saritas,B. Momeni and G. Hohenfeld,
l- - - ll valtrate iv iv ac
,,/*o isovaltrate iv ac
Aduheration or natural aariabilityi, Enantioselectiue gas - \l oRr homovaltrateI iv ic ac
chromatography inpurity control of essential oils.!. High Reiol.
dienevalepotriates homovaltratell ic ic ac
Chromatogr.,20(2),55-61 (1997).
acevaltrate aciv iv
M. Holla, E. Svajdlenka,J. Tekel, S. Vaverkova and E. Havranek, or iv aciv ac
Contposition of the essential oilfrom M elissa officinalis L. anltiaated cH2oR3 homo acevaltrate acic iv ac
in SloxakRepublic.J. Essent.Oil Res.,9, 481-4S4(1997). or iv acic ac
T. van den Berg, E. Fruendl and F-C. Czvgan, Melissa officinalis r---f)
subsp. altissirna: characteristics and. possible adulteiation of
lemon balm. Pharmazie,52, 802-808(1997).
.,Q(Yo Monoenevalepotriates
didrovaltrate iv ac
S.Hose,A. Z:inglein,Th.vandenBerg,W. Schultze,K-H. Kubeczka monoenevalepotriates homodidrovaltrate ic ac
and F-C. Czygan, Ontogenetic Dariotion of the essentialleaf oil a) Valepotriatestructures wnere
oJ'Melissafficinalis L, Pharmazie, 52, 247 -253 (1997).
iv = isovaleryl
ic = isocapryl
Valerian Oil
ac = acetyl
The roots and rhizomesof the Yaleriana sDeciesare used to aciv = acetoxy-isovaleryl
prepare phytomedical preparations that can be taken as acic = acetoxy-isocapryl
sedatives.These plants include Yaleriana fficinall,s L.S.I.
(European valerian),V rvallichii DC and V edulis Nutt ssp.
procera F.G.W. Meyer. Although the valerian root active
compounds that possesssedativeproperties have not been r4cooR
fully characterized,they are generally believed to be the b) Methyl (R = CH3)andvalerenic
valerenate acid(R= H)
essential oil, the valepotriates and valerenic acid and its
Figure 1. Structuresof valepotriatesand valerenic
derivatives(Bos and Woerdenbag, 1996). acid
Although this review is directed at the essentialoil, it is of
interestto know the stmcturesof the valepotriates(vanMeer
and Labadie, 1981) and valerenicacid (Bos et al., 1997a). Two years later, Chen and Gu (1989) used both GC and
(SeeFigure 1.) CC/MS to examine the chemical composition of valerian
In 1971, Schaetteanalyzeda number of cultivars of V root oil produced in China. The compoients they identified
officinalis . Llthough he did not present any quantitative data, in the oil are summarizedas follows:
he dld identify the following constituentsin the oil:
cl-thujene(0.43%) 1 ,1- d i m e t h o x y - 3 , 7 - d i m e th yl - 2 .6 -
cI-prnene borneol cx,-pinene (5.46%) octadiener(0.3S%)
campnene ixterpineol camphene(23.50%) B-gurjunene (0.38%)
p-pinene B-caryophyllene B-pinene(3.50%) 4(2,6,6-trimethylcyclohexa-1,3-
myrcene eremophilene p-cymene(0.40%) dienyl)but-2-en-4-ensr (0.98%)
limonene B-bisabolene limonene(O.77%) decahydro-2,2,4,8-tetramethyl-
1-terpinene y-cadinene 7,7-dimethyl-2-methylene- 4,8-methanazulen-9-olt (0.44o/o)
bornylformate zingiberene bicyclo[3.1.1]heptanet decahydro-1, 1,4,7-tetramethyl-
bornylacetate vareranone (1.37o/o) cyclopropazu len-4-s1tQ.32%)
bornylisovalerate 3-methyl2-norbornane- B-caryophyllene alcohol(0.50%)
carboxaldehydet (0.35%) 2,6-dimethyl-6(4-methyl-3-
A root oil of V tfficinalis var. latfolia produced from camphor(0.33%) pentenyl)-2-cyclohexene-1
plants grown in Guizhou province was subjectedto GC/MS i s o b o r n e o(l1 . 3 1 %) carboxaldehydet(0.60%)
analysisby Long et al. (1987).The components{bund in the 2-isopropyl-5-methyl anisole 4- elhy12,2,4-Irimethyl-3-
(0.28%) (1-methylethenyl)cyclohexane-
oil were as follows:
bornyl acetate(46.22%) methanotr(1.99%)
isovaleric
acid (0.23%) borneol(0.38%) isobornylacetate(0.61%) ledol(0.53%)
o-thujene(0.11%) terpinen-4-ol
(0.19%) carvyl acetate*(1.64%) bornylisovalerale (0.72%)
cr-pinene(6.76%) myrtenol(0.12o/o) 2,2,4-trimethyl-3- geranylisovalerate(0.61%)
sabinene(0.60%) methylthymol(0.12%) cyclohexene-1 -methyl (22)-3,7-dimelhyl-2,6-octadien- 1-
B-pinene(6,48o/o) bornylacetate(50.56'l.) acetatet(0.61%) ol isovalerate(1.52%)
myrcene(0.99%) carvylacetd€- 9.47%) 1,4-dimethoxytetramethyl-
Iimonene(1.77o/") 6-elemery>(0.17o/o) benzene(0.17%)
5-2-carene(O.04%) dihydrocarvylacetate(1.620/0)
" correct isomer not identified;t tentative identification
allo-ocimene*(0.01%) B-caryophyllene(0.38%)
camphor(0.05%) cr-humulene(0.11%) This is a tlpical example of an analysisrvhere the author-s
"correct isomer nol identified used a computerized MS matching program to identifv the
componentsof the oil. In the list of comporindsa 'terltati\ e
267
identification' designation has been added to the authors' Table Vll. Comparative percentage
data. This reviewer believesthat all of these tentative iden- composition of two root oils of
tificationsare mis-identificationsbasedon the computerized Valeriana officinalis var. sambucifolia
"best fit." As a result, of the 28 compoundscharacterized,at
Ieastnine are wrong. Compound Root Oil A Root Oil B
In 1993,Zhuetal. reported the resultsof an analysisof V tricyclene <0 . 1 < 0.1
fficinalis root oil of Chineseorigin. The compoundsidenti- (t-prnene 0.8 7 .3
fied in this oil were: sjenchene 1.1 8 .9
campnene 1.0 8 .6
o-pinene(7.41"/") bornylacetate(44.17'/.) nexanal <0 . 1 <0 .1
camphene(32.08%) pthujolt (1.70/") 0.3 1 .8
B-pinene
B-pinene(4.39%) B-caryophyllene (0.10%) sabinene <0 . 1 0.3
p-cymene(0.82%) B-gurjunene (0.34'/") myrcene <0 .1
limonene(1.73'/.) aristola_1,9-diener(0.98%) o-phellandrene <0 .1
borneol(0.76%) valeranonone (0.10%) o(-terpinene .0.'| <0 .1
p-t.butylbenzyl
alcoholt lrmonene <0 . 1 1 "8
(0.37'/.) p-phellandrene 0 .8
yterpinene <0 . 1 o .7
r probably misidentified components
p-cymene <0 . 1 0 .3
Two years later, Grdnicher et al. (1995) analyzed the terpinolene <0 .1
nexanol <0 . 1
comnosition of the steam-distilledroot oils of nine-month-
6-elemene 8.5
old field-grownY. fficinalis L. var. sambucifulia Mikan fil. bicycloelemene <0 .1
(r)-.V officinalis L. ssp.sambucifolia Mikan fil.) Celak in <0 . 1 0 .5
F-selinenet
Switzerland. Usins GC and GC/MS as their methods of methylcarvacrol 0 .5
analysis,the authors compared the composition of the oils bornylacetate i.u I J.J
268
Tabfe Vlfl. Percentage composition of the rooUrhizome
oils ot Valerianaofficinatis
269
Table lX. Percentage composition of Table X. Percentage composition of the
Valeriana officinalis leaf oils from ltaly headspace and oil ol Valeriana officinalis flowers
0. 14 0. 14 t tetraclecane t-
B-p he llan dre ne
(E)-2-hexenol I 1.46
isovalerate 1.80
citronellyl 1.59 t.ov
p-methylanisole 20.54 7.51 3.60
amylvalerate 1.12 0.18 2.22
furfurol - 0.50
cr{erpineol 0.95 3.54 aF^
octyl acetate 1.73 I-
bornylacetate 21.59 33.39 0.40 n 6 n ti a l a n tn a 2.06 0.66
isobornylacetate 0.26 0.69 0"84 benzaldehyde t I-
ofV. fficinalis from three collection sitesin ltaly. The results Y-D. Chen and C-H. Gu, Stud4 on the chemical composition of
essential oil from Yaleriana offi,cinalis. Lincnan Huaxue Yu
of this study are shown in Table IX.
Gongre,9(1),59-64(1989).
It is also perhaps of interest to note that Brunke et al.
L. CoassiniLokar and M. M oneghini, Ceogr aphical oari ation in the
(1992) compared the headspaceanalysisof the flowers of V
monoteryenes of Valeriana officinalis leaf. Biochem. System
fficinalis with the dlstilled oil. Their results can be seenin EcoL. 17, 563-567 (1989).
summary form in Table X. E. 'J. Brunke, F. J. Hammerschmidt and G. Schmaus,Tha headspace
analq sisof Jlow er fragrances. Dragoco Rept., ( I ), 3-3f ( f 992).
R. Schaette,Zur WertbestimmungPharmakologieund umtaelt-
bedingtenWlrkstofibildungaon RadixValerianae.PhD. thesis, L-F. Zhu, Y-H. Li, B-L. Li, B-Y. Lu and N-H. Xia,Arom atic Plants
Univ.Miinchen(1971). and Essential Constituents. South China Institute of Botany.
.*. ChineseAcademyof Science;Hai FengPublishing Co. &stributed
J. H. van Meer and R. P. Labadie, and retsersed-
Straight-phase
' by PeaceBook Co., Ltd. Hong Kong (1993)
phasehigh perfonnanceliquid chrVmatographic seporationsof
aalepotriateisomersand homologues. j. Chromatogr', 205,206- F. Grdnicher, P. Christen and I. Kapetanidis, Essential oils from
212( 1981) . normal nndhairy rootsofYaleri'ana officinali'saar. sambucifulia.
Phytochemistry, 10, 142l-1424 ( 1995).
C-2. Long, H-L. Xiao andJ-Q. Peng,Thechemicalconstituentsof
the esiential oil from the roots of Valerianafficinalis oar. j-J. Xian, G. Yuan, Y-X. Zhang, J-M. Yuan and X-W. Lto, The
' -
latifolia.YunnanZhiwuYanjiu,9(i), 109-112(fg87). chemicol constituents of tEe essential oil from the roots of
270
Valeri.ana fficinalis. Yunnan Zhiwu yanjiu, lT, 47g-4gl
(1995). Table Xl. Percentage composition of
U. Ravid,-E. Putievsly and I. Katzir, Stereochemical analysis of hyssop oils and extracts
borneol in essential oils usingpermethylated B-cyclofuxtrin as a
chiral stationary phase.Flav.'Fragr. _Zf,tbi-iSS (fSSO). Autumnharvest Springharvest
J"
S. Gobbata and E. Lolla, A new HpLC method Compound oi l Extract
for the analysis of Oil Extract
ualerenic acids inValeriana officinalis extra&s. Fltoterap"ia,61,
o-thujene 0.22 0.17 0.21
159-162(1996).
0-pinene o.47 0.17 0.42
R. Bos, H. J. Woerdenbag,H. Hendriks, H. Zwaving,p. A. G. M. campnene
J. 0.11 r 0.10
DeSmet, G. Titel, H. V. Wikstrcim andJ. C. Schefler,Analytical sabinene
J. 1. 1 0 1.36 1 .3 1
o.spc:t2ol phyt otherapeut ic uolerian p iepa rat ions.phy,toc,hem.
Anal.7. I43-l5l (l 996). B-pinene 8.85 4.78 8.23 4.07
4,7- dimethy| 4 -octano It 0.20 0.33 0.09
R. Bos and H. J. Woerdenbag , Analytical aspectsofthe essentialoil, myrcene 2.20 1.18 1.98 1 .2 4
aalerenic acid deriaatit:es and oalettotriaies in Valeriana limonene+ o. | / 3.07 5.13 3 .1 9
fficinalis roots and rhizomes. In: proceedings, lntentational B-phellandrene
Symposium on breeding research and mediciial and aromatic
(E)-B-ocimene 0.77 1.31 1.07 t
plants. Edlt., F. Pank.-p. 355-358, Beitrlige zur Zuchtungs-
terpinolene 0.09
forschung, Quedlinburg, Germany (1996)." t 0.18
linalool 0.61 0.70 0.64 0.42
R. H.
!_os, J. Wo_erdenbag,H, Hendriks,W. H. Kruizinga, J. K. pinocamphone 22.82 8.14 31.23
Herrema and ]. J. C. Scheffer, Methql aalerenate, a neu
isopinocamphone 43.29 55.17 40.64 39.21
sesqui-terpenoid in the essentialoil from underground parts
myrtenol 0.92 3.21 1.07 2j2
of Valeriana fficinalis L.S.L. Zel{. Naturforsc"h, S2c,' BEg-
86 0 (1 99 7a ). B-caryophyllene 2.74 0.17 1.99
s-humulene 0.45 t 0.35
R. Bos, H. J. Woerdenbag, H. Hendriks C. Scheffer,
""d I. I.
C_omposition^ofthe essential oils from underground
allo-aromadendrene 1.20 r 't . 6 6
parts of germacreneD
Valeriana fficinalis L. S.L. and seu-eralcloselqrilated taxa. Flai. 9.02 0.61 9.00 t
bicyclogermacrene 4.gg 0.29 5j2 t
Fragr.J., 12,359-370(1997b).
myrtenylmethylether 1.60 0.43 5.12
t probablyincorrectidentification;
t = trace (< 0.01%)
HyssopOil
In 1992, Jean et al. compared the chemical composition of dihydroverbeno ner (0.4%) (E)-anethole(0.3%)
hyssopoil produced by hydrodiffusion from plants harvested pinocarveol.(0.6%) sabinylacetate.(0.3%)
at two times of the year (spring and autumn) with hyssop isopinocampho ne (17.4%) methyleugenol(0.5%)
pinocamphone (18.1%) B-bourbonene(1.2%)
extractsproduced by microwave hexaneextraction. Analyses
terpinen-4-ol(0.4%) B-caryophyllene (.a%)
of the oils and extracts were done using GC (for reteniion oterpineol (0.2%) a-humulene(0.1%)
indices and quantitative data) and GC/MS (for component myrtenol(1.3%)
identityconfirmation). The resultsof this study are shownin
- correctisomernot identified:
Table XL r probablyan incorrectjdentificatron
t = trace(< 0.1o/o)
Three yearslater, Venskutonis(Ig95) used GC and GC/
MS to ana)yzetwo samples of hyssop oil produced from This sameyear, Garcia Vallejo et al. (1gg5) reported the
plants grown in Lithuania. The oils were determined to composition of an unusual sample of hyssop oil produced
contain: from plants collectedin Cuenca(Spain).Analysisperformed
a-thujene(0.22-0.230/o) 1,8-cineole (0.32-0.47"/") by using a combination of GC and GC/MS revealed that the
-pinene(0.52-0.63%) (E)-B-ocimene(0.79-2.76o/o) oil contained:
camphene (0.11%) othujone(0.05-0.07%) tricyclene(O.22%) o-thujone(t)
sabinene(1.56-1.74%) Bthujone(0.17-0.20./.) o-thujene(O.21%)
(11.09-11.24o/") pinocarvone B-thujone(0.05%)
B-pinene (1.92-1.Sgo/o) o,-pinene(2.54%) camphor(0.10%)
myrcene(2.47-3.49%) pinocamphone (14.87-29.16%) camphene(0.17%) trans-pinocarveol(0.64%)
oterpinene(0-0.02%) isopinocamphone(13.20-2B.E4o/") verbenene(0.05%) pinocamphone (0.15%)
p-cymene (0-0"02%) methytchavicot (O.19-2.87o/") sabinene(2.97Y") pinocarvone(1.72%)
limonene(0.80-1.22%) B-caryophyilene(0.56-1.84%)
B-pinene(16.82%) myrtenylmethylether (1.21%)
p-phellandrene myrcene(1 .68%) isopinocamphone (3.12%)
+ myrcenol
(7.88-12.670/0)
o-phellandrene(trace) terpinen-4-ol(1.28%)
p-cymene(0.15%) uterpineol (1.00%)
This sameyear, Bourrel et al. (19g5) examinedboth the
limonene(2.250/") myrtenal(0.50%)
antimicrobial characteristics and cherdcal composition of 1,8-cineole (52.89%) myrtenol(0.44%)
hyssopoil. Using GC/MS, the authotrsdetermined rhat the (Z)-p-ocimene(1.44%) B-terpinylacetatet(t)
oil possessedthe following composition: (E)-B-ocimene (1.3S%) sabinylacetate.(t)
y-terpinene(0.29o/") B-bourbonene(0.34%)
o-pinene(t) p-"yr"rtA1o.tu.; ci+linalooloxidefuranoid(t) (0.1B%)
B-caryophyllene
B-pinene(0.2%) B-phellandrene (0.2%) terpinolene (0.19%) a-cadinene(t)
myrcene(t) linalool(0.6%) linalool(0.26%) o-humulene(t)
27r
Table Xll. Comparative percentage composition of oils produced from
different Hyssopus species at selected maturities
Species and
Stage of maturity a-pinenea 1,8-cineole pinocamphone isopinocamphone isopinocampheolo
H. montana
0. 9 0 .8 40.6 25.6 9.8
pre-flowering 18.7 6 .8 36.5 zz. I 3.1
fullflowering ' 16. 5 to.u 37.4 15.5 J.+
post flowering 19. 5 14. 8 45.1 9.1 1.5
H. meretacens
4. 1 2. 5 17.4 53.5 3.5
pre{lowering 5. 9 3. 2 12.1 55.6
fullflowering I l.Ct 5. 4 6.3 58.4 2.7
post flowering 2. 6 1. 3 16.4 48.3 4.0
H. aristatus
11. 7 R1 56.1 0.3
pre{lowering 12.4 6 .3 3t.J 10.5 2.7
fullflowering B. B 61.7 8.5 2.1
post flowering 7. 5 5 .7 67.8 4.9
H. canescens
5. 9 1 .9 3.5 73.7
pre{lowering 12.4 2 .0 0.8 73.8 1.1
fullflowering 18. 9 3 .1 1.0 69.3 1.0
post flowering 9. 3 0 .9 o.4 92.6 0.4
H. officinalis
fullflowering 2. 2 3 .2 50.5 17.9 3.2
a misidentification
of 0-pinene;0 misidentification
(0.08%) elemol(t)
allo-aromadendrene B-pinene ( 2 . 9 1 - 3 . 3 1 %) isopinocamphone (0.97-1
.45%)
germacreneD (t) spathulenol(0.12o/o) myrcene(1.27-1.65%) B-bourbonene(0.95-1.1
7%)
y-cadinene(t) T-cadinol(0.07%) limonene(4.99-6.02%) e (2.62-3.46'k)
B-caryophyllen
6-cadinene(t) 1,8-cineole (11.92-14.91o/o) (1.24_1.97%)
cr_cubebenet
" correct isomer not identified:
linalool(49.00-51 .65%) oxide(1.71-3.18%)
caryophyllene
1 probably incotrectidentification p i n o c a m p h o n(e0 . 4 8 - 1 . 0 1 %)
t = trace (< 0.01%)
r misidentificationbased on incorrectelutionorder
Also in 1995, Bodrug et al. compared the composition of
oils produced |rom Hyssopusfficinalis L., H. montana L., In contrast the oil produced from Italian plants was found
H. meretacensDubjansky,H. aristatus (Jads.)Bric1.and H. to contain a more tlpical composition such as:
canescensNyman (Hqssopus, 1977) at various stages of
cr-pinene(0.58%) B-bourbonene (1.43'/.)
maturity. A summary of this study can be seenin Table XIL
B-pinene(11.15%) methyleugenol(4.01%)
A survevof the published literature revealsthat H. mont(tno myrcene(2.13%) (1.5a%)
B-caryophyllene
and H. n'r,eretacens are not found in the most recent flora. limonene(12.18o/o) cx-cubebener(2.20%)
Also, H. canescensshould be more correctly knou'n as H. pinocamphone(1.72o/") caryophylleneoxide (0.50%)
isopinocamphone (43.26%)
fficinalis ssp.canescens(DC.) Briq. and H. aristatus as H.
officinalis ssp.aristatus (Godron) Briq. As a result, because t incorrectidentificationbased on incorrectelution order
of the anomaliesfound in the report of Bodrug et al., it is the
belief of this reviewer that not a lot of scientific value can be Also in 1997.Vereset al. found that the oils obtained {rom
gained from it. nine collectionsof H. officinalisgrown from seedof diflerent
TWo years later, Salvatore et al. (1997) examined the sourcescould be categorizeddependingupon their percent-
chemicalcompositionof sixoils of H. ofriainalis v ar.deanmhens agecompositionof p-pinene, limonene, pinocamphoneand
collectedaroundBanonin the Haut-Alpesregionof Provence isopinocamphone. The oils were rich in either isopino-
(France) and one oil produced from H. officinalis harvested camphone(5->507o),pinocamphone(3- >507o)or contained
in Piedmont (Italy), the Italian sideo$theHaut-Alpes region. F-pinene and limonene (I->60Vo) as major components.
Analysis of the six oils from Banon by GC and GC/MS Hgssopus.ln: Flora of the USSR.Vol. XXI, Edit., B. K. Sishkin,
showedthat they contained: translatedbyN.Landau,pp. 320-329,
KeterPubl.Houselerusalem,
cx-pinene(2.23-2.71%) camphene (1.72-2.03%) U. S.Dept.Commerce, VA (1977).
NTIS,Springfield,
272
F. I. Jean, G. J. Collin and D. Lord, Essential oils and microuaae cr-+ B-phellandrene myrcene(0-9.7%)
extracts of cuhia at ed pl ant s . Perfum. Flav., I 7(3 ), 35-4 1 ( 1992). (1.1-75.0o/ol bornylacetate(0.9-22.0%)
P. R. Venskutonis, Essential oil comltosition of some herbs cultiaated camphene(t-8.0%)
in Lithuania. ln: Flauours, Fragrancis ond Essential Oils. t = trace (< 0.1%)
Proceedingsof the 13th International Congress of Flavours,
Fragrances and Essential Oils, Istanbul, Turkey, Oct. 1995, The following year, Bambagiotti et al. (1981) used a
Edit., K. H. C. Baser,Vol. 2, pp. 108-123,Anadolu Univ. Press, combination of column chromatography,GC, IR and MS to
Eskisehir, Turkey (1995).
examine the oxygenated and sesquiterpenoid fraction
C. Bourrel, G. Vilarem, G. MichelandA. Gaset,Etudedespropridtds (8.07ool the whole oil). The compounds identified in this
bacteriostatiques et fongistatiques en milieu solide de 21 huiles
fraction were:
essentiellesprdamblement analqsdes.Rivista Ital. EPPOS, No.
1 6, 3-1 2 (1 99 5) . benzaldehyde(0.04%) borneol(0.15%)
2-decanone(0.02o/o) d-terpinylacetate(0.59%)
M. C. Garcia Vallejo, J. G. Herraiz, M. j. Perez-Alonsoand A. phellandral (0.13%)
pinocamphone (0.10%)
Velasco-Negu eruela,Yolatile oil of Hyssopus fficinalis L. from piperitone (0.05%)
Spai,n.l. Essent.Oil Res.,7,567-568(1995). cls-p-menth-2-en- 1-ol
(0.05%) carvone(O.O2%)
M. Bodrug, M. Miron, N. Marcu and I. Dragalin, Biologlcal cr{enchylalcohol(0.07%) citronellylisobutyrate(0.02%)
characteristics and component structure of the oil obtained bornyiacetate(1.95%) ct-muurolene (0.06%)
-Bul.
from Hyssopus introduced into Moldoua. Acad. Stiinte terpinen-4-ol(0.78%) citronellol(0.22%)
Republ. Moldova, Stiinte Biol. Chim., (3), 1t-15 (1995). methylthymol (0.23%) bornylisovalerate(0.08%)
G. Salvatore,M. Nicoletti,V. DiGiola, R. CiccoliandA. D'Andrea, 2-undecanone (0.08%) cuminaldehyde (0.08%)
Characterisation chimique de L'huile essentielle de hysope frans-p-menth-2-en- 1-ol 6-cadinene (0.09%)
(Hyssopus fficinalis L.) aaridtd decumbensdesAlpes de Haute- (0.08%) p-cymen-B-ol (0.14%)
Prooence (Banon, France). Rivista Ital. EPPOS, (Numero (0.16%) citronellylisovalerate(0.03%)
B-caryophyllene
Speciale),672-681 (1997). myrtenal(0.05%) citronellylvalerate(0.02%)
1-undecen-1 O-one(0.05%) caryophylleneoxide (0.05%)
K. Veres, E. Varga,A. Dobos, Zs. Hajdu, I. Math6, Zs. Pluhdr, E.
pinocarveol* (0.16%) humuleneoxide.(0.03%)
N6meth and J. Berndth, lnuestigation of the composition of
2-decenal*(0.04%) a-multijugenol (0.1B%)
essentialoils of Hyssopus fficinalis L.1lopulations.In: Proceed.
(E)-anethole(0.04%) ethyl cinnamate(0.03%)
27th lntemational Sympos.Essent. Oils, Yienna, I 996, Edits.,
citronellylacetate(0.06%) T-cadinol(0.22%)
Ch. Franz, A. Math6 and G. Buchbauer, pp. 2L7-220,Allured
cryptone(0.37"/.) T-muurolol(0.21%)
Publ., Carol Stream, IL (1997).
o(,-terpi
neol (0.87o/o) s-muurolol(0.08%)
o'humulene(0.04%) s-cadinol(0.39%)
Dwarf Pine Oil
Dwarf pine oil (known as "Latschenkieferolen" in Austria
where it is produced), which is alsoknown as mugo pine oil
In 1983, Latish et al. examined the composition of the
or pumilio pine oil, is obtained by steam distillation of the
needle oils of severalPinusspecies.Amongst these analyses,
needle-rich twigs and small branches of Pinus mugo Ttrra
the authors reported that an oil of P ffrugo was found to
(rp. P montana Mill., P pumilio Haenke, P. mugo var.
contain:
pumilio (Haenke) Zenari).
In 1972, Bambagiotti et al. used preparative distillation, B-terpineol-(t) (t)
terpinolene
GC and IR to identify 11 monoterpenes and seven o,-pinene(32.0%) bornylacetate(3.1%)
camphene(11.7o/o) B-caryophyllene (0.8%)
sequiterpenesin the hydrocarbon fraction of mugo pine
B-pinene(28.4%) (t)
longifolene
oil. The componentsidentified were: myrcene(5.0%) o-humulene ( 1 . 6 %)
s-prnene p-cymene 6-3-carene(t) (1.7%)
cx-terpineol
campnene terpinolene crterpinene(6.4%) 1-muurolene(t)
limonene(t) 6-cadinene(2.9%)
B-pinene B-caryophyllene
myrcene oc-humulene B-phellandrene (t) y-cadinene(0.6%)
6-3-carene y-muurotene 1,8-cineole(t) chamazulene (3.1%)
0-terpinene g-muurolene 'correct isomer not identi{ied
limonene cr-selinene t = trace (< 0.1%)
R-qalinana
B-phellandrene
y-terpinene y-cadinene In 1986, Yatagaiand Sato reported that the needle oil
of P. pumilio was determined to contain the following
Although the authors did not present any quantitative data, constituents:
they did showchromatogramsof the Crofraction and the C,,
santene(O.17%) l i m o n e n e( 9 . 1 3 %)
fraction. From these chromatograrns it was possible to tricyclene(0.38%) rene (0.42'/.)
B-phelland
deduce that the major monoteryene and sesquiterpene cr-pinene(9.95./") yterpinene (O.23%)
hydrocarbonswere 6-3-careneand y-cadinene,respectively. camphene(5.24%) B-ocimene- (0.33%)
p-pinene(1.20./") p-cymene(0.09%)
In 1980,Glasland Wagner repor,trdthat the main cornpo-
sabinene(0.30%) p-mentha-2,4(B)-diene (0.07%)
nents in dwarf pine oil were:
6-3-carene (11.77%) terpinolene (2.15%)
santene(0-0.20%) o- + B-pinene(11.6-74.1%\ myrcene(1.52%) (Z)-3-hexenylacetate(t)
c{,-terpinene
(0.13%) a'cubebene(0.33%)
273
o(-copaene (0.62'/.) germacreneD (7.62%) tricyclene (0.3-2.3%) 6-3-carene(7.6-33.2%)
B-bourbonene (0.13%) cr-muurolene (1.87%) o-pinene(7.9-22.8%) nene (0.2-0.7'/")
o,-terpi
linalool(0.07%) O-cadinene + geranylaceiate camphene(1.1-4.4o/") p-cymene(0-02%)
linalylacetate(0.10%) ( 11. 8e% ) sabinene(0.5-1.2%) limonene(0.7-6.8%)
bornylacetate(0.43"/") calamenene* (0.13%) B - p i n e n (e1. 5 - 1 9 . 0 %) rene(2.4-18.0'/")
B-phelland
terpinen-4-ol(0.39%) spathulenol(0.24o/o) myrcene(1.7-21.5%) (0.3-0.9%)
T-terpinene
B-elemene (4.81%) T-cadinol(2.17%) oc-phellandrene (0-1.1%)
B-caryophyllene. (0.40%) o-muurolol(1.51'/')
cx-humulene (0.86%) bisabolol-(t) The authors further reoorted that thev had characterized
cr{erpineol(0.10%) d-cadinol(5.82%) y-cadinene and spathulenol ln the 11 needle oils, 16 twig/
*correctisomernotidentified branch oils, 13 branch oils and 21 commercial oils. These
t = t r a c e( < 0 . 1 % ) results are shown in Table XIV.
One year later, Kubeczka and Schultze
( I987) analyzed a number of oils ofvarious Tabfe Xfff. Percentage composition of various oils of Pinus mugo
coniferae. They found that a commercial
sample of P. mugo ssp. pumilio (mugo Gompound 1 2 3 45
pine) contained: sanlene - r-0.2
tricyclene(0.40'/.)
0.3-1.6 0.3-2.7 t-0.4 t-0.6 0.2-1 .5
o-pine ne(1 3.1 0% ) d,-pinene 7.9-22.8 7.8-23.9 1.2-9.6 0.4-9.3 4. 1- 31. 5
camphene(1.75%) camphene 1.1-4.4 1.1-6.8 t-0.9 0-0.8 1. 3- 6. 7
B-pinene(7.63%) sabinene 0.6-1.1 0.2-0.8 0.6-3.3 0.4-2.4 t-1.7
sabinene(0.63%) B-pinene 1.5-18.3 1.0-15.1 1.2-24.8 0.9-4.1 1. 3- 20, 7
6-3-carene (35.18%) myrcene 1.7-21
.5 1.3-9.8 1.5-36.3 2.1-23.9 0. 5- 7. 0
myrcene(5.04%) a-phellandrene 0-1.1 t-1.3 0-0.5 t-0.5 0. 1- 1. 3
cr-phellandrene(0.54'/.)
o(-terpinene (0.58%) 6-3-carene 8.0-33.2 7.9-26.7 0.8-43.3 13.5-45.3 0.5-30.1
limonene(5.62%) o-terpinene 0.2-0.7 t-1.1 0-0.3 t-0.3 0.2-4.5
rene(15.02'/.)
p-cymene 0-0.2 0-0.8 r-0.7 t-0.6 0.4-6.9
B-phelland
y{erpinene(0.57'/.) limonene 0.7-5.4 0.7-15.8 0.8-26.6 0.7-1 .7 6.1-37.1
(E)-B-ocimene (0.33%) B-phellandrene 4.6-15.0 0.7-6.8 6.9-39.7 11.0-24.4 0.5-16.5
p-cymene(0,72o/") B-ocimene- 0-t 0{ 0t 0-t 0-0.4
terpinolene (3.59%) yterpinene 0.3-0.9 0.3-1.6 r-0.7 0.3-0.5 0.1-5.0
0-copaene+ 0-cubebene(t) terpinolene 0.1-5.6 2.0-9.6 0.7-4.6 2.1-4.8 1. 0- 29. 2
bornylacetate(1.25'/.)
e (3.32%)
linalool 0-0.2 0-0.6 0-0.2 0-t 0-0.2
B-caryophyllen
o,-humulene (0.46%) terpinen-4-ol 0 . 4 - 1. 1 0.7-3.4 t-1.0 0.3-1.2 0. 2- 1. 5
germacreneD (0.50%) crterpineol 0.3-1.5 0.5-2.9 t-0.6 t-0.9 0.3-4.5
8-cadinene+ y-cadinene(0.43o/.) methylthymol 0.2-0.7 0-0.4 t-1.6 0.6-1.3 0- 0. 4
T-cadinol(t) hnrn\/l anctetc 1 5-7.8 3.8-16.7 r-4.3 0.3-2.4 1.0-7.9
T-muurolol(t) cxterpinylacetate 0.6-2.1 1.1-7.7 0.3-2.6 1.1-2.3 0- 0. 4
0-cadinol(t) 0-copaene 0-0.2 0-0.2 t-0.2 t-0.8 t-0.2
B-elemene 0.2-0.9 r-0.7 t-1.0 0.1-0.8 0- 0"2
B-caryophyllene 3.0-9.0 0.5-2.5 3.0-12.6 5.6-11.7 t - 2. 5
In 1988,Maurer and Hauser identified o.-humulene 0.5-1.9 0.2-0.8 o.7-2.4 0.9-2.9 t-0.9
the presence of u,-terpinyl isobutyrate in cx-muurolene 0.7-3.7 0.5-2.2 0.3-4.2 0.4-8.2 0-0.7
Pi,nusmugo leaf oil. 8-cadinene 0.6-4.3 | . t- o.c 0.2-4.7 0.3-3.3 r - 1. 0
Eight years later, Kartnig et al. (1996) caryophylleneoxide 0.2-0.5 0.1-0.7 0.2-3.1 .8
0.5-1 0-0.8
examinedthe composition of oils produced *correctisomernot identified;t = trace (< 0. 1%)
ga/1
M. Bambagiotti A., F. F. Vincieri and G. Cosi, Monoterpene and M. YatagaiandT. Sato,Terpenesof leaf oilsfrom confers.Biochem.
t-nlgyit:r? uryg drocarbons of Pirrusmugo. phytochemistrT. I l, System.Ecol.,14,469-478(1986).
!-y
1455-1460 (1972).
K. H. KubeczkaandW. Schultze,Biologyand chemistryof conifer
H. Glasl and H. W-agner,Gaschromatrographische (Jntersuchung oils.Flav.Fragr.J.,2,137-I48(1987).
rs_onArzneibuchdrogen (1) 7. Mitt.- iC UntersucLrung aoi
B. Maurer and A. Hauser, Idenffication de certains produits
Pinaceen-Olen des Handels und Versuche zu ihrer
aromatisants dansdesar6m.es.parfum.Cosmet.Ar6mei,No. 82.
Standardisierung. Deut. Apoth. Ztg., i20(2), 64_67 ( 1980).
69-72(1988).
M. Bambagiotti A., S. A. Coran, V. Giannellini, F. F. Vincieri and G.
Th. Kartnig, U. Fischerand F. Bucar,Vergleichenfugaschromn-
Moneti,-lnuesti,gation of Pirrus mago essential oil crxygenated
t9graphischeUntersuchungenanLatscheikteferrtlen.Sci.phann.,
Jraaionby combineduseofgaschromatographyand dryTolumn 64.487-496(1956).
chro matography. Planta Mad.. 4J, 39-45 ( t'gSi ).
V. G. Latish, R. D. Kolesnikova and R. L Deriuzhkin, Essential oils
Th. Kartnig,U. FischerandF. Bucar,Vergleichenfu
gaschrom.atog-
of s_omepine speci_es.In: 9th Inte rnatio nal-Congressof Essential
yphls-cheUnterwchungenan Latschenkreferatei. 2. Min eituig.
Oik, Essential Oil Technical payterBook 2. pp.E3-8g, Singapore
Sci.Pharm,65,289-297(1997).
(19 83 ).
275
Progress in Essential Oils
& Flavorist,
fromPerfumer
Reprinted 1999,Yol.24,No.4, P. 31
July/August
ties for either the fruit or leaf oils, although t = trace(< 0.1%)
the fruit oil was slightly more active than the leaf
276
Table ll' Comparative percentage composition of the aliphatic hydrocarbons found
in the leaf and bark distillates of Hamamelis virgiiiana
ofthis plant can be found in the review that appeared in 1g53 The following year,Martelli et al. (1g78) used GC and GC/
(Fulling). According to Leung and Foster, pharmaceutical MS to examine the volatile composition of Hamamelis leaf
preparationsare obtained from the leaves,branch tips and water distillate. The compounds identified were:
bark and solid and fluid extractsof each are sold commer- nonane CI-terpineol
cially. In addition, bark and leafdistillates are also available oecane borneol
commercially, It is this latter area that is the subiect of undecane benzylalcohol
dimethylbenzene- thymol
this rerriew.
trimethylbenzene- carvacrol
In 1977,Martelli used thinJayer chromatographyto ten- methylethylbenzene. eugenol
tatively identify the following compon_entsin commercial methylisopropylbenzene* dihydroactinodiolide
samplesol Hamamelis leai diltiilate wfier, diethylbenzene. diisobutylphthalatet
o,-ionone* (Z)-3-hexenol dibutylphthalatet
carvac16l
hexanol ethylstearate
B-ionone. 2-hexenal-
6-methyl-5-hepten-2-one 1-octen-3-ol o,-ionone*
2-hexehbl-
eugenol linalool
3-hexenol*
.
* correct isomer not identified
correct isomer not identified t artifacl
277
Table lll. Comparative percentage composition of the diterpene and sesquiterpene hydrocarbons
found in the leaf and bark distillates ol Hamamelis virginiana
Recently, Engel et al. used GC (retention indices) and E. H. Fulling, American uaitch hazel - history , nomenclature and
modernutilization. Econ. Bot., 7, 359-3Bf (1953).
GC/MS (spectralcharacterization)to examinethe composi-
tion of the steam-distilledvolatilesof the leavesand bark of A. Matelli, Hamamelis water (distilleduater of Hamameli'sairgin-
iana Linnoeus) 7stnote: Charocterizationby thinlayer chroma-
H, oirginiana. Becausethe authorsidentified approximately
togrophy. Rivista ltal., EPPOS, 59, 528-533 (1977).
170 components in both the leaf and bark distillates,their
A. Martelli, C. Bicchi and F. Frattint, Homamelis water (distilled of
results have been grouped together according to the types Hamnmelis uirginiana Linnaeus) 2nd note: Identification of the
of components identified. As a result, the aliphatic hydro- essential oil components by CLC and GLC-MS. Rivista Ital.,
carbonscan be found in Table II, the diterpene and sesquit- trPPOS, 60. 26r-264 (1978).
erpene hydrocarbons in Table III, the aliphatic aldehydes A. Y. Leung and S. Foster, Encyclopedi,a of commnn natural
in Table IV the aliphatic ketones in Table ! the aliphatic pp. 513-514.Wiley
ingredieits usedlnfood, drugs and cosm.e.tics.
alcoholsin Table VI, the acids and estersin Table VII, the IntersciencePubl., New York (1995).
monoterpenesin TableVIII, the oxygenatedsesquiterpenes R. Engel, M. Gutmann, C. Harisch, H. Koloclziej andA. Nahstedt,
Stidg on the com,positionof the aolatile fraction of Hamamzlis
and diteruenes in Table IX and the miscellaneous com-
airginiana. Planta Med., 64, 251-258 (1998).
pounds in-TableX. From these data, itean be seenthat there
is a higher proportion of the orygelLatedconstituents in the
bark distillate than in the leaf distillate; therefore, the bark
distillate must have the stronger a{ema.
278
Table V. Comparative percentage composition Table Vl. Comparativepercentagecomposition of
of the aliphatic ketonesfound in the leaf and the aliphatic alcohols found in the leaf and bark
bark distilfates ol Hamamelis virginiana distif fates ot Hamamelis virginiana
Table Vll. Comparative percentage composition of the acids and esters found
in the leaf and bark distillates ot Hamamelis virginiana
Total 7 .2 1 7. 8 1
t furanoidform
t = trace(< 0.01%)
280
Yl a ng Y lang O il
composition of a dttilled oil of ylang ylang flowers with
Using multidimensional GC/MS and a chiral column, volatile concentratesalso produced f;; fre"shylang ylang
Bernreuther and Schreier (1g96) determined that the flowerseitherby SDE orsupercriticalfluicl extraction(Spn
l.
enantiomeric distribution of linalool in ylang ylang oil was Using CC (retention indices)and GC/MS (componenrcom_
( R)-(-) -linalooI (70.6To): ( S)-(+ "
)-linalooI (zS.4E")
. position confirmation by MS), g0 constituentswere charac_
In 1995, Stashenkoet al. examinedthe volatile constitu_ terized in either the oil or the extracts. These results are
ents ofylangylang flowers grown in Colombia using GC and summarized in Table XII.
GC/MS. Flowers were harvestedat three differenistaees of In 1997, Talou et al. reported that the heart of the
maturity and their volatile concentrates *ere prod.rcld bv ylang ylang aroma could be describedasbeing floral, sweet,
simultaneous distillation and extraction (SnE) using bakamic andwoody, although in a sampleof yiangylang otl,
methylene chloride as the solvent. The constituents founJ the only components characterized by these u,rth*orsi,"."
in the volatile concentrates of flowers harvested at different germacrene D and an o-farnesene isomer.
maturity stagescan be seen in Table XI. Also in 1997,Casabiancaet al. used 13C/12C isotoperatios
The following year,Stashenkoet al. (1996)compared the to examinethe genuinenessof various commercialiamples
Intermediate Fully
Intermediate Fulty
Young maturity mature Young maturity mature
green green yellow
Compound green green yellow
tlowers flowers flowers Compound flowers flowers flowers
2-methyl-3-butenol - 0. 14 0.07 4-(2-propenyl)-phenol
3-methyl-2-butenol - 0.08
0.06 methyl4-methoxybenzoate - 0.06
3-hexenol" o.21 butylbenzoate 0.03 0.08
2-hexenol**"
3-methyl-2-butenylacetate
0.89
0.78
0.28
0.33
geranylacetate
o[-copaene
i,, 2.99 1 .9 6
benzaldehyde 0.37 0.21 0 .1 3
0.94 4-methoxyphenylmethylacetate - 0 .1 1
cr-pinene 9.64 2.85 1.87 s-yrangene 0.54 0.27 0 .1 6
campnene 1. 30 0.03 tetradecane 28.14 12.25 5.51
B-pinene 3.03 0.90 u. ot) B-caryophyllene 5.46 3.69 1.69
myrcene 0.49 0.24 0.16 cinnamylacetate***
(Z)-3-hexenyl 1.42 2 .0 9
acetate 0 .1 3 0.16 isoeugenol** 0.25 1.03 0.37
P-methylanisolet 0.34 o. \tu 9.65 B-cubebene 0.17 0.91 0.58
benzylalcohol o.23 0.43 2.20 B-bourbonene 0.19
1,8-cineole 0.32 0. 14 0.09 cr-humulene 2.29 1.25 0.74
limonene 0. 11 0.07 3-buten-2-ylbenzoate o.20 0.71
(E)-B-ocimene 0. 16 0. 18 0.14 methyleugenol o.tt 1.98 0 .8 6
2-methoxyphenol o.17 germacreneD
methylbenzoate
11.23 /.uo 5 .5 5
- 3.20 6.50 ymuurolene
p-cresol 0.37 0 .1 9 0 .1 4
0.09 o(-amorpnene 0.17 0.10
linalool 0 .1 3
20.95 38.97 35.49 (E,E)-o{arnesene
phenylacetonitrile 1.47 1.06 2 .3 4
-t 0.14 6-cadinene 0.18
benzylacetate 0 .1 6
0. 15 4.78 11 . 6 3 y-cadinene :'o
ethylbenzoate - 0 .1 2
1.46 (Z)-3-hexenylbenzoate -
2-methoxy-4-methylphenol :" 0 .1 9
0.07 (E)-nerolidol 0.17
methylsalicylate 0 .1 3
- 1 o.29 caryophyllene oxide
tx-terpineol - 0.07
0.25 0 .1 3 0.14 s-bisabolol
3.4-dimethoxytoluene
o.ut 0.08 0.07
0 .1 3 0.17 cedrol 0.16
1,4-dimethoxybenzene 0. 1 3 cr-muurolol
nerol 0.23 0.18 0 .1 1
0 .1 0 0.27 cadinol. 0.62 0.16
2-phenyl-1-nitroethane 0j2
o.20 cadinol* 1.27 0.23 0 .1 2
anethole*** 0 .1 7 0 .2 7 0.35 T-muurolol 0.09
cinnamylalcohol.." -I 0.26 (E,E)-farnesol 1.58 1.1I 0.84
methyl2-methoxybenzoate 0.05 benzylbenzoate
methylanthranilate A 7. 2 1 6 .1I
0.08 (E,E){arnesylacetate 0.44 o.28 0.61
benzylbutyrate 0.04 benzylsalicylate 0.48 0.51 1 .3 7
'correct isomernot identified
"' presumedto be (Z)-isomer
"'presumed to be (E)-isomer
r also knownas p-cresylmethylerner
t = trace(< 0.01%)
281
ofylang ylang oils and concretes.The results ofthis study ylang extra asshownin Table XIV As can be seenfrom these
are shown in Table XIII, using the following formulation: results,the commercial samplewaseither alower qualityof
ylang ylang 3rd or a higher quality oil with some synthetic
r.^ I ro' linalool added.
c rr ^ n,
? |frf u/ -t_
l( r r c / r 2 Co f < ' o mp o u n idn q u e s ti o n )-lx This same year, Olivero et al. (1997) used quantitative
L , t3 g l t2 go l s ta n d a rd ) structure retention relationships (QSRR) to examine the
fragrance value of ylang ylang oil components. For para-
The same authors also examined the enantiomeric ratio meters, they used retention indices for 48 components of
of (R)-(-)-linalooland (S)-(+)-linaloolin the samesamples ylang ylang oil which were empirically predicted from
ofylang ylang oil and concrete, and compared these results calculated and exoerimental data on molecular structure.
with synthetic linalool and a commercial sample of ylang Furthermore, they determined information such astopical,
Table Xll. Percentagecomposition of the oil and extracts of ylang ylang of Colombianorigin
282
Table Xlll. variation of 513c0/oolevels of some specific constituents of various
ylang ylang oils and 6bncretes of differint grades and origins
Compound '1 2 3 7 I I 10
prenyl acetate -zo.u -2o.3 -26.1 - zt - c - - 2b.5 -32.2 to -32.5
p-methylanisole -31.0 -31.9 -31 .3 -30.1 -27.B -30.0 -30.8 -29.2 -29.2 -29.2 to -30.6
linalool -31.4 -31.3 -32.2 -29.4 -31 .1 -31.6 _e1 A -31 .1 -30.6 -26.0 to -34.0
B-caryophyllene -26.5 -27.B -27.2 -26.8 -31 .5 -25.6 -26.9 -27-0 -26.8 -31.1 to -32.2
methylbenzoate -29.6 -29.6 -29.8 -28.5 -27.8 -28.1 -30.8 -28.1 to -31 .0
benzylacetate -30.3 -29.3 -30.7 -27.5 -28.9 -27.1 -32.4 -28.6 -28.6 -26.4 Io -31.7
cinnamylacetate -29.3 -30.9 -ot.1 -27.1 -28.7 to -28.9
benzylbenzoate -3 1 .1 -3 0 .8 -30.8 -29.4 -30.1 -29.2 -30.1
-5t.2 -30.7 -25.1 to -26.6
benzylsalicylate -32.9 -32.2 -31.9 -32.1 -32.6 -31.4 -30.8 -30.7 *30.3 -26.0 to -26.9
Legend:
YlangExtra,Comoros;2' YlangExtra,Mayotte;3. YlangExtra,Madagascar;4. YlangExtra,Commercial; ylang
5. Concrete,Comoros;
6' YlangConcrete,Madagascar;7. Ylang3rd, Comoros;B. Ylang3rd, Mayotte;9. Ylang3rd, Madagascar;
10. Variationof naturalidentical
substancesfrom differentsources
283
Cistusand Labdanumlsolatesand Extracts oils are the traditional direct-fired water/steamdistillation,
According to Vacchiano (1992), Cistus ladoniferu,sL. var. high-pressuresteam distillation, and atmospheric continu-
moculahtsDunn is the only cistusplant used for the produc- ous distillation. Oils produced by the traditional method
tion of cistusisolates.In Spain,the majorproducing country are rich in monoterpenes.As one might expect, they have
the area in which this speciescan be found is greater than poor odor tenacity. Oils produced by high-pressuresteam
1 million hectares, in practically all regions except the distillation possessall of the important odor- characters
northern humid zones. However, it should be noted that of the plants; however, because of the high pressure
C.Iadanferus can be found growing throughout the Medi- experiencedduring distillation, burnt and cooked notes are
terranean countries in uncultivated areas, in particular often associatedwith these oils.
associatedwith pine forests. Oils produced bv continuous steam distillation also
All cistus isolates are obtained by processing the har- contain ull of the important odor charactersof the plants,
vested branches using either steam distillation or solvent but becauseof the long residencetime of the plants in the
extraction. In contrast, all labdanum isolatesare obtained still (24 h) (Vacchiano,1992), the oil, which is produced in
from the gum that is exudedto protect the plants during the a little less than0.LToyield (fresh weight basis),has a higher
hot, dry summer. According to Vacchiano(1992), two pro- odor value.
cessesare used to collect the gum. These processes,which In 1972, Tabacik and Bard determined that a benzene
are different, are known asthe "Zamorean process"and the extract of labdanum gum contained the following diterpenoid
"A ndalucianDro('ess'. compounds:
The Zamoiean processis used in the province of Zamora methyl13,14-dihydropalustrate
in the triangular area of Zamora-Benevente-Montebuey methyldehydroabietate
between the regionsof Salamancaand Leon. In this process Iabdan-Bcr-,15-diol
groupsofS-10 twigs are cut at 1 m lengths,bundled together labdan-8cr-.
15.19o-triol
and Ieft for several days to dry. trach bundle is successively The authors also identified B-sitosterol and B-acetoxy-
immersed with the tender tips down into four drums of geraniol in the same extract.
boiling water (ca. 200 L) for a short period of time. The In 1984, Boelens reported the results of his analysisof
water is kept boiling by direct fire. The boiling water causes labdanum oil. Althoush he noted that the oil contained 160
the gummy exudateto melt. Becauseit is lighter than water, components, he was ibl" to characterize more than 757o
it is skimmed off the surfaceand exnressedto rernove rnclst of the oil. The compounds identified were:
of the retained water. The crude gum produced this way,
which is produced in a yield of approximately2-2.57o(fresh 1,3,3-trimethylcyclohex-1-
myftenal(0.8%)
e n e ( 0 . 1 %) 2,2,6trimethylcyclohexanone
weight basis),retains approximately207oH2O. o-pinene(4.9%) (2.0%)
In contrast,in the Andalucian process,bundles of 18-20 camphene(1.4%) 3,5,5-trimethylcyclohex-2-enone
branches,1-1.5 m long, are successively immersed for 10 u{erpinene(0.2%) (0.6%)
minutes in a 200 L drum filled with 2.57oNa2CO3solution p-cymene(2.1%) acetophenone(t)
o-p-dimethylstyrene (1.9%) heptylvinyl ketone(2.9%)
held at 60-70'C. The solution is filtered to remove exrrane-
germacrene D (1.0%) camphor(0.3%)
ous materialssuch asleaves,and other plant pieces.Then it allo-aromadendrene (0.8%) pinocamphone (1.3%)
is charged into two clean drums where it is left to cool cx-selinene (6.4%) pinocarvone(0.4%)
overnight. The following morning the filtered solutionsare cr{enchylalcohol(0.2%) octyl vinyl ketone(0.2%)
neutralized with sulphuric acid and the precipitated crude borneol(1.3%) verbenone(1.2%)
terpinen-4-ol (1.8%) isopiperitenone (0.2olo)
gum is removed with a perforated skimmer to allow easy
p-cymen-B-ol(0.3%) carvotanacetone (0.3%)
removal of water. The crude gum obtained in a yield of o-terpineol(2.4%) 3-phenylproprionic acid (22.2%)
3.0-3.57o(fiesh weight basis) with a water content of 10- palustrol(0.7%) cinnamicacid (1.4%)
257aisthencreamed or made homogenousin a small heated viridiflorol (1.4%) ocimenylacetate*(0.2olo)
container.Becausethe yield of crude gum is higher from the dehydro-1,8-cineole (0.6%) bornylacetate(2.1%)
rose oxide* (0.8%) p-cymen-8-ylacetate(0.3%)
Andalucian process,this is becomingihe favored method of
caryophylleneoxide(4.4"/") methyl3-phenylpropionate (0.2%)
crude gum collection. Prior to processingthe crude gum ambrox(0.4%) benzyl3-phenylpropionate (1.7%)
into an extract, water removal is performed using vacuum
evaooration.
t = tr ac e {< 0.1% )
The majority of crude labdanum gum is solvent
ertracted to produce a resinoid (direct ethanol extraction), The following year, Escher (1985) identified B-homocy-
a concrete (hexane or rarely benzene extraction) and an clogeranicacid as a trace constituent ofcistus Ieafoil. Two
absolute (ethanolic extract of conerete).A limited quantity years later, Regino et al. (1987) harwestedplants of Cistus
is also distilled or co-distilled dirqctly from the crude gum. ladanferus L. from three different regions of Portugal. Oils
Cistus oil is produced by steam'distillation of harvested obtained by hydrodistillation were analyzedby GC and the
cistusbranches.The three processesused to produce these results ofthese analvsescan be seen in Table )O/.
284
Table XV. Percentagecomposition of Table XVf. Effect of drying of Cisfus ladaniferus
Cisfus ladaniferus leaf oil produced from plants plants on the oil percentagecomposition
harvestedin three regions of Portugal
Compound Fresh plant oil Dried plant oil
Compound RioFrio Muge Grandola
O,-plnene 41.5 41.4
thymol 2.44 - 4.26 2.03 - 3.76 0.83 2,2,6-trimethylcyclohexanone 5.0 5.5
carvacrol 0.32 - 0.59 0.99 - 1.87 0.57 c-campholenic aldehyde 2.4 2.6
e ug en ol O . 22- 0. 53 0 - 1. 09 0.26 bornylacetate 2.5 2.6
isoeugenol* 0.17- 0.36 0 - 0.64 0.26
ledolt terpinen-4-ol 1.1 1 .1
7.70 -11.15 7.78 -13]8 6.59
myrtenol 0.8 0.8
* correctisomernot idenliJied frans-pinocarveol 1.2 1.5
I tentativeidentification carvone 0.6 0.7
viridiflorol 3.6 4.s
ln 1991,Li et al. examinedthe cl1'na11iq lieadspaceof the 15-nor-8-labdanol 0.3 0.5
lreslrll' h;111'ssted
leavesand tr,vigsof C . ladaniJenr,s
grorvnin
ChinausiriganXAD tr:rp.Therrntrldesorptionofthe trappecl
The iruthors fbund that the leaf oil of C. lrrlaniftnts
volatiles,r,vithsubsequentGC, GC/MS and GC-FTIR, re-
var. nvrculotrls wils quantitatively very sirnilar to that of
sulted in the characterizationof the folkl,ving constituents:
C.ladaniftru.s var. albiflnrtts. In adclition, the authors also
toluener(7.61%) 3-ethylstyrener(1.21%) cletermined that tlie aerial parts (leaf) oil composition rvas
2,3,5-trimethylhexa-1,3- 1,3-diethylbenzenel 1OB0%; very sirnilar irrespective of rvliether the har-vested plants
dienet(0.66%) frans-roseoxide (0.82%)
6-methyl-2-heptanonet camphor(1.70%) rvere fresh or dried (see Table X\,/I). Finalh., the authors
(2.13%) 2,4-undecadiensl-t (1.00%) identi{iecl manv con'lpounds in C. lodattifr:rlis for rvhich
o-pinene(31.27%) pinocamphone (1.15%) quantitative data u'as not obtained. These compounds can
camphene(4.05%) isopinocamphone (10.49%) be seen listed :rs follows:
rx-thujenet(0.56%) borneol(1.52%)
Bterpinenet(0.43%) naphthalener (0.80%) toluene calacorene.
6-methyl-5-hepten-2-one 3-methylnopinone (0.80%) 1,2-dimethylbenzene hexanal
(0.36%) verbenone(1.04%) 1,3-dimethylbenzene methyl-2-heptanone
6-isopropylidene-bicyclo bornylacetate(0.50%) 1-ethyl-2-methylbenzene octanal
[3.1.0]hexanet(0.48./.) cr-muurolene (0.61%) 1,2,3{rimethylbenzene 2-octanone
2,2-dimethylcyclopentyl patchoulene*t (0.76%) 0-p-dimethylstyrene isophorone
ketonet(0.16%) o-copaenet(0.81%) dimethylnaphthalene- 6-methyl-5-hepten-2-one
p-cymene(2.37%) longifolenet (0.447") caoalene p-menth-1-en-9-al
2,2,6trimethylcyclohexanoney - m uur olene( 1. 19% ) methylcyclohexane fenchone
(2.14o/") o-guaienet(0.38%) 1,4-dimethylcyclohexane camphor
limon en e(1 .01 % ) 2,6-di{ert.butyl-4-methylphenolt 1-nonene isopinocamphone
diethylbenzene.t ( 1.58%) (0.4e%) oooecane pinocamphone
isophorone(2.66%) b-cadinene (0.51%) nenercosane tagetone
diethylbenzene.r (0.77%) junipercamphort(1.09%) tricosane 2-undecanone
4-ethylstyrenet(2.64%) heptacosane aceTopnenone
tricyclene veroenone
* correct isomer
not identified piperitone
r misidentificationbased on either incorrectretentionindex or computer assisted B-pinene
lvlS interpretation sabrnene p-methylacetophenone
p-menthatriene* cuminaldehyde
A ye:rrl:rter,Vernin et nl. (1992) used GC and GC/NIS to cr-terpinene isopiperitone
determine the main constituentsof a letrfoil of C. loclanifent,s B-phellandrene p-mentha-1,3-dien-7-al
var. albiflonr,s collected in tlie Esterel region of southern T-terpinene 2-hydroxy-6-methylacetophenone
terpjnolene cinnamaldehyde
France. The components identified rvere as {bllou's:
o-menth-8-ene B-damascone*
cr-pinene (56.0%) terpinen-4-ol(0.8%) a-vll nnona 4-(3-hydroxybutylidene)-3,5,5-
ca mph en e(1 .9% ) myrtenal(0.6%) s-cubebene trimethyl-2-cyclohexanone
limon en e(1.7 % ) frans-pinocarveol(0.8%) o-copaene ^Pii l ^ r ^u^u^a r ".,.
,l
vyr d u vl d r v
1,8 -cin eo le
(0 .2% ) allo-aromadendrene + (Z)-3- cr-gurJUnene frans-sabinylacetate
p-cymen e(1 .2% ) hexenyltiglate(0.7%) calarene cls-sabinylacetate
2,2,6-trimethylcyclohexanone
carvonelO.3%) B-caryophyllene urD-udr vyr duvtdtu
(2.5%) myrtenol(0.6%) germacrene D geranyl2-methylbutyrate
cis-roseoxide (0.3%) trans-earveol(0.2k) eremophillene 3-phenylpropylacetate
lrans-roseoxide (0"3%) palustrol(0.1%) cr-muurolene 3-hexenylbenzoate*
c-campholenic aldehyde ledol(0.7oo) 6-cadinene 2-phenethyl
3-phenylpropionate
(2.3%) (2.9%)
viridiflorol calamenene* hanzrrl hanznrfo
bornylacetate(2.1%) 15-nor-8-labdanol (0"4%) cr-calacorene geranyl3-phenylpropionate
285
(Z)-3-hexenol o,-cadinol 3,3,5-trimethylcyclopent-4-enyl-(1,2)-y-lactone
linalool o-muurolol 1,3,3-trimethylcyclopent-4-enyl-(1,2)-y-lactone
hotrienol ci+anhydrolinalooloxide g-campholenic acid
cls-pinocarveol (furanoid) y-campholenic acid
o(-terpineol linalooloxide- a-campholenic aldehyde
borneol furfural 1-campholenic aldehyde
sabinol* 5-methylfudural ethylo-campholenate
p-cymen-8-ol 2-methyl-5-isopropylphenol ethyly-campholenate
(E)-cinnamyl alcohol eugenol camphonanic acid
R-ar rdacmal isoeugenol* camphonanylmethylketone
viridiflorol tetradecanoicacid 1-(1',2',2'-Irimethylcyclopentyl)-hexa-2,5-dione
spathulenol ethyl1-(2',2',3-trimethylcyclopenta-1,3-dienyl)-propionate
2-methyloctanoic acid
* correct isomer not identified
cls-roseoxide
The following year, Vernin (1993) used fractionation lrans-roseoxide
cis-vitisoirane
and GC (retention indices) and GC/MS to characterize lrans-vitispirane
four 3-phenylpropionatesin an oil of C. ladaniferus. The 3,7-dimethylocla-2,4,7-trienol
compounds characterizedwere: 3,7-dimethylocta-2,5,7-trienol
2-phenethyl alcoholand its homologs
geranyl3-phenylpropionate 9-oxodamascone
3-phenylpropyl
3-phenylpropionate jasmolactone
2-phenethyl
3-phenylpropionate tuberolactone
dehydrogeranyl
3-phenylpropionate (Z)-tagetone
In 1994,labdanumwasreviewedbyOhloff. Inhis review, raspberryketone(4-hydroxy-phenyl-2-butanone)
3-methoxy-4-hydroxy-phenyl-2-butanone
Ohloff relied heavily on an unpublished study in which 3,4,4-trimethylcyclopentan-1,2-dione
Escher reported that she identified approximately 250
compounds. According to Ohloff, labdanum oil was found The structures of some of the less commonly encoun-
to contain only 10 compounds at concentrationsin excess tered compounds listed by Ohloff can be seen in Figure 1.
of I.07o. The main constituentswere: Two years later, Guy and Vernin (1996) isolated a f raction
of C. Iadanifetus oil of French origin that was rich in acids
o-pinene(6.8%) (Z)tagetenone(1.8%)
and phenols. After methylation, the methyl esters of the
camphene(1.4%) allo-aromadendrene+ ledene
pinocarveolt
(1.8%) (3A%\ following acids were characterized:
bornylacetate(1.2%) ledol( 1. 1% )
(3.7%) 3-methylvalericacid pentadecanoicacid
borneol(1.1%) viridiflorol
2,6,6{rimethylcyclohexanone 4-methylvalericacid methylpentadecanoic acid*
(1 -7% ) hexanoicacid hexadecenoicacid*
methylhexanoic acid. hexadecanoicacid
t probablythe trans-lorm methylheptanoic acid methylhexadecanoic acid*
methylheptenoic acid- methylhexadecanoic acid*
Other constituents for which no quantitative data octanoicacid heptadecanoicacid
presented were as follows: nonanoicacid octadecenoicacid
octadecanoicacid
3,7-dimethylocta-2,6-dienoic
amorox acid eicosanoicacid
6-oxo-isoambrox decanoicacid methyleicosanoicacid.
3-hydroxy-decadihydro- naphthalene
1,3,7,7tetramethyl
undecenoicacid" benzoicacid
labdanolicacid undecanoicacid dihydrocinnamicacid
oxocativinicacid dodecanoicacid y-campholyticacid
and isomers
3,5-dimethylsalicylaldehyde
methyldodecanoic acid- u-campholyticacid
2-hydroxy-S-methylacetophenone and isomers y-campholenic
methyldodecanoic acid- acid
2-hydroxycuminaldehyde and isomers geranicacid
tridecanoicacid
2-methoxy-3,5-dimethylbenzaldehyde methyltridecanoic acid
acid- a-campholenic
2-methoxy-5-methylacetophenone
methyltetradecanoic acid. myrtenicacid
2-methoxycumi naldehyde
methyltetradecanoic acid"
3,4,5{rimethylphenol
4-vinylphenol
B(9)-dihydrocarvacrol
I E-hant-2-an^li.la In addition, Guy and Vernin identified a seriesof phenols
1,5-oct-2-enolid@ 7s. which were identified as the following methyl ethers:
1,5-non-2-enolide
1,5-dec-2-enolide(massoialactone)- antsole methyl4-vinylguaiacol
methylB-orcinolcarboxylate o-methylanisole methyleugenol
thujonicacid p-methylanisole methylvanillin
] heptan-
myrtenicacid or 3,3,7-trimethylbicyclo[4.1 veralrole elemicin
1-carboxylicacid p-dimethoxybenzene methylpropiovanillone
3,3,4trimethylcyclopent-4-enyl-(1,2)-ylactone methylchavicol coniferaldehyde
286
",t?^^|t:*"S;;" ,il;^"Q;"
.."\zo
\sl
l0
H
pv" ll 12 l3
'.-X.z--2" ><AA
trl
\J 1.,". \-
-
l4
tl
o4o/-z/:':./
^
l8
287
Tabfe XVff. Comparative chemical composition (%) ol various groups ol Cistus ladaniferus oil
A year later, Mariotti et al. (1997) analyzedan oil of the In addition, the authors determined the composition
leavesof C. Iadanferus using l3C-NMR spectroscopy(for of oils produced from 20 different plants collected from
component identification) and GC on two capillary columns the wild in Corsica. The oils were analyzed in the same way
of different polarity (for quantitative and component identi- aswas the compositerepresentativeoil samplewhose com-
fication verification by retention indices). The authors noted position is listed above. Examination of the results of the
that the 13 most abundant compounds were characterized various oil analyses reveals that the oils can be grouped
by direct l3C-NMR of the whole oil, while the other 32 accordingto their compositionsinto six types.A summary of
components lvere only characterized by 13C-XMR of the oil variations in these si-rtr,oescan be seenin Table XVII.
fractions produced after fractionation using flash chroma- AIso in 1997, Mrabet er al. used GC and GC/MS to
tography and gradient solvent elution. The components compare the chemical composition of oils of tlvo varieties
identified in the oil of Corsicanorigin were: o{ C. ladaniferous gtown in Morocco. The results of this
o-pinene(39.0%) acetophenone (0.2%) study are summarized in Table XVIII.
camph en e(2 .1% ) (E)-B{arnesene(t) More recently,Weyerstahl et al. (1998) used a combina-
B-pinene(0.5%) o-humulene(t) tion of analyticaltechniques to carefully examine the com-
sabinene(0.8%) isoborneol(0.2olo)
y-muurolene (0.4%)
position of a commercial sample of labdanum oil. They
oterpinene(0.1%)
limonene(1.7%) myrtenylacetate(0.4%) reported that the oil contained more than 300 constituents,
B-phellandrene (0.4%) borneol(0.8%) and they identified 154 neutral and 32 acidic constituents.
yterpinene (0.4%) aterpineol(0.5%) The neutral compounds were as follows:
p-cymene(1.7%) ledene(0.9%)
terpinolene (0.2%) verbenone(0.3%) S-methylfudural(0.2%) cis-linalooloxidefuranoid(0.2olo)
2,2,6-trimethylcyclohexanonecarvone(0.3%) (0.2%)
6-methyl-5-hepten-2-onelinalool
(0.e%) 6-cadinene(0.8%) (0.1% ) nonanal(0.1% )
cyclosativene (0.7%) y-cadinene(0.4%) p-cymene(0.4%) oxide(0.2%)
cls-rose
o-copaene (0.8%) geranylacetate(0.3%) 2,2,6-trimethylcyclohexanoneo-campholenic aldehyde(0.3%)
cr-campholenic aldehyde myrtenol(0.4%) ( 1 . 3 %) lrans-roseoxide (0.1%)
(0.8%) trans-carveol(t) 2,6,6trimethylcyclohex-2- (E)-3-nonen-2- one (0.7%)
cr-gurjunene (0.3%) caryophylleneoxide (0.4%) enone(0.3%) c a m p h o r( 0 . 1 %)
isopinocamphone (0.5%) ledol (3.3/a) acetophenone (0.1%) trans-pinocarveol (1.e%)
pinocarvone(0.9%) globulol(0.3olo) trans-linalooloxidefuranoio frans-sabinol(0.1%)
bornylacetate(3.1%) (11.8%)
viridiflcnol (o.4%) (E)-tagetone(0.2%)
t erpin en -4-o(1l .1%) spathulenol (0.5%) 6,8-epoxymenth-1 -ene (pinol) neroloxide (0.2%)
myrtenal(0.5%) B-eude'vnol(0.5%) (0.8%) pinocamphone (1.5%)
allo-aromadendrene(1.9%) 1s-acetoxylabdan-8-ol(t) cr-p-dimethylstyrene(1.0olo) pinocarvone(0.3%)
frans-pinocarveol (1.9%) y-campholenic aldehyde propiophenone (0.1%)
(0.3%) (Z)iagetone (0.2%)
t = kace (< 0.1%)
288
Tabfe XVllf. Comparative percentage composition of Cisfus ladaniferusvar. atbiflorus
and C. ladaniferusvar. maculatus
- correctisomernot identified
t incorrectidentification
basedon elulionorder
t = trace(< 0.05%)
2E9
\H
2l 22 24
25 26 27 28
A .{i\
.iY ^{
29 30 3l 32
n
33 34 35 36
37 38 39
Figure2. Furtheruncommon
labdanum oil constituents (Weyerstahlet al., 1998).
21. 1, 1, 6t r im e th y l -1
,2 -d i h y d ro n a p h th a l e n e 31. B-oplopenone
(dehydro-ar-ionene) 32. muurola-4(10),14-dien-1-ol
22. is oledene 33. 4-isopropyl-6-methyltetral-
1-one
23. cr-ambrinol 34. 5,11-epoxycadin-1('l0)-en-9-ol
24. aromadendr-1-ene t* 35 ambrox
25. c ubeb- 11-e n e sesquichamaneol (1,1O-seco-1-hydroxycalamenen-1O-one)
26. 6,6,10-trimethyldeca-2-one 37. drim-8-en-7-one
27 . ar omadendr-1( 10)-en-9-one,(sguamulosone) 38. 1-epi-3,4-dehydroviridif
lorol
28. 5, 11- epox y c a d i n(1 -10 )-e n e - 39. 14,15-di-nor-8,13-epoxylabd-12-ene(sclareoloxide)
29. gleenol 40. 15-nor-labdan-8-ol
30. c ubeban -'1l -o l
290
7- acely12,2,6-Irimethylbicy- B-oplopenone (0.1%) o,-campholytic acid (0.3%) geranicacid (2.4%)
clo[4.2.0]octan e (0.2o/o) ledol( 1. 3% ) y-cyclogeranic acid (0.9%) decanoicacid(3.8%)
isoledene(0.2%) copaborneol (1.B%) y-campholenicacid(1.4ok) 3-isobutenyl-5-methyl-5-
cx,-copaene (1.1%) 3,4-dehydroglobulol (0.3%) nonanoicacid (1.6%) vinylbutyrolactone(0.9%)
methyleugenol (0.4o/o) 6-acetyl-5,8,8- B-cyclogeranic acid (1.0%) undecanoic acid(0.3%)
1-(fur-2-ylmethyl)-2{ormyl- trimethylbicyclo[3.2. 1]octan- c-camphoneicacid(2.1%) lauricacid(2.5%)
pyrrole(0.1%) 2, 3- dione( 0. 1% ) davanicacid (0.7%) dimethyl(Z)-2-hexyl-3-
dodecanal(0.2%) muurola-4,1 0(14)-dien-1 -ol (0.3%) 2,6-dimethyl-5-oxoheptanoic methylbutendioic acid (1.7ok)
o,-ambrinol(0.2%) 1-epi-cubenol (0.4%) acid (1.2%) myristicacid (2.7%)
dihydro-B-ionene (0.1%) y-eudesmol (0.2%) dihydrocinnamic acid (6.5%) palmiticacid (5.1%)
geranylacetone (0.1%) o-muurolol(0.3ol.) 1,5,5-lrimethylbicyclo14.
1.01 oleicacid(1.2%)
aromadendr-1 -ene (0.9%) B-eudesmol (0.4%) heptan-7-carboxylic acid A linoleicacid(1.0%)
cubeb-11-ene(0.7%) cr-cadinol(0.6%) (o.7%) stearicacid(0.8%)
4,4,7u-trimelhyl- 1,4,5,6,7,7a- cadalene(0.5%) l,5,5trimethylbicyclo[4.1.0] labd-B(17)-enoic acid (5.1%)
hexahydro-2H-inden-2-one copabornylacetate(0.6%) heptan-7-carboxylic acid B labd-7-enoic acid(6.3%)
(0.1 % ) 4-isopropyl-6-methyltetral-1 -one ( 1 . e %) labd-B-enoicacid (4.0'/.)
tuberolactone (0.1%) (o.2"/") myrtenicacid(6.0%)
massoialactone(0.1%) pentadecanal (0.1%)
allo-aromadendrene (1.5%) 5-epi-1, 10-seco-aromadendran-
(E)-B-ionone (0.2%) 1, 1O - dione( 0. 1% ) C. Tabacik and M. Bard, Etude chimio-taxononique dans le genre
tridecanal{0.1%) 9-hydroxyladanifer-1 0-one Cisfi.r.s.
Phr,tochemistry,f0, 3093-3109 (197f ).
'1,1,5,6-tetramethyl-1
,2- [9(10(1)-abeo-9-hydroxy-
dihydronaphthalene (0.6%) M. H. Boelens, Aromatic prochtctsfrom Cistus ladanferu,s L. In:
aromadendran-1 0-onel (0.1%)
cls-calamenene (0.5%) De,stillaciones
Bordas Chinchrtrreta SA. SevilleSpain,Information
1,1O-seco-aromadendran-1 ,
1,5-cls-aromadendr-9-ene booldet11994.7.
10-dione(0.1olo)
(1A% ) (Z)-3-hexenyl dihydrocinnamate S. Escher, cited in I. Flament and G. Ohloff, Volatile constituents
ledene(9.3%) ( 0. 1% ) of algae Odoriferou,s constituents of seaueeds and structure of
1-(1,2,2-trimethylcyclopent-1 - hexyldihydrocinnamate (0.3%) nor-teryenoids idznffied in a sakusa-noriflarour. In: P,rogres,s
in
yl)-pentan-1,4-dione (0.2%) aromadendr-1 (10)-en-9-one Flaaour Research -ZgB4.Edit. f. Adda, Elsevier Science Publ.,
dihydroactinidiolide (0.2%) (squamulosone) (0.3%) A m s t e r d a m1 1 9 8 5 , t .
1,1,5,6{etramelhyll.2.3.4- 5,11-expoxycadin-1 (10)-3n-9-ol M. B. Regino, S. Frazao, M. M. Carmo and F. Venancio,Estu&tda
J.
tetrahydronaphthalene (0.2%) pat'te rclatil do concreto de esteaa (CisttLs Ladanifer L.) ent
(o.2%) ambrox (1.4o/") comparacaocom o( oleo e,ssencial. In: 2as lornadas Nacionaisde
6,6,10-trimethyldecan-2- sesquichamaenol (1,10-seco-1 - Planta,s Aromaticose Oleo.sEsscniatis.pp. Sf-SO.Lisbon (1987).
one (O.2k) hydroxycalamenen-1 0-one)(0.1%) G. Li, Y-Q. Zheng and Y-L. Sun. Studie,son the frogrant aolatilized
4,7-dimethyltetral-1 -one drim-8-en-7-one (0.1%)
constituents of Cishn Iadan i;fenrs.Fenxi Ceshi Tongao, lO e), 12-
(0.2%) 10-hydroxycalamene-8,9-epoxide rE(199t).
6-cadinene(0.4%) ( 0. 1% )
frans-calamenene (0.6%) 6-acetoxy-11-nor-drim-7-en- C. Vacchiano, Distillation/extraction of Ci,stus labdanum and its
s-calacorene(0.6%) 9-one(0.2%) application in p erftLmery.Indian Perfurn.. 36( 2 ). 134-143 (I 992).
11-nor-driman-B-ol (0.3%) '15-nor-labd-1 (17)-ene(0.6%) G. Venrin, M. Bemard and j. Metzger, Analgsis of ci,stusoil (Cistus
B-elemol(0.2%) 15-nor-labd-8-ene (0.5%) ladanlftrus L. albiJloru,s antl maculatus) from E*erel u,sing the
(E)-nerolidol (0.2%) 6-oxo-isambrox (0.1%) CC/MS databank. Changesin oolotile oil compositittnat diJferent
1,2-dehydroviridiflorol (1.4%) 15-nor-labd-7-ene (0.5%) dzaelopmennl stuges.In: Pro ceedingsof 12th Intem ational Congress
palustrol(1.2olo) 14,15-di-nor-8, 13-epoxylabd- of Flaaours, Fragrancesand Essentiul Oils,Vienna -1992.Edits.,
1,2-dehydroglogulol (0.2%) 12-ene(sclareoloxide)(0.2%) H. Woidich and G. Buchbauer,(Post-Congress Volurne),pp. B0-
6-ptolylheptan-2-one(0.2"/") 15-nor-labdan-B-ol (0.7%) 104Vienna (1992).
5,11-epoxycadin-1 (10)-ene 8-epi-1 3-nor-ambreinolide G. Vernin, MassspectraanclKoaatsindices of someplrcnqlpropanoic
(0.8%) (isosclareolide) (0.1%) acid e,stersfound in the essential oil of Cistus ladaniftnn L.,
gleenol(0.5%) 13-nor-ambreinolide (sclareolide)
'1-epi-3,4-dehydroviridif J. Essent.Oil Res.,5,563-569(f993).
lorol (0.2%)
G. Ohloff, Scent and fragrance,s.Thefascination of odors and,their
(0.2o/o) manoyloxide(0.3%)
chemical pers2tectit:eslTransiated Ly W. Pickenhagenand B. M.
globulol(0.2%) 13-epi-manoyl oxide(0.3%)
Lawrence,pp. 238, SpringerVerlag,Berlin (1994).
viridiflorol(4.3%) labd-8(17)-en-1 5-ol(ladenol) (0.4%)
cubeban-1 1-ol(4.1%) labd-7-en-15-ol (0.4o/o) L Guy and G. Vemin, Minor compounclsfrom Cistus ladaniferus L.
tetradecanal (0.1%) labd-8-en- 15-ol(0.3%) es,sential
oil.fronLEsterel.2. Acidsandphenols.l. Essent.Oil Res.,
8.455-462(1996).
t = trace (< 0.1%)
J. P. Mariotti, F. Tomi, J. Cassanova,j. Costa and A. F. Bernadini,
Some further structures of less commonlv encountered Composition of the e,ssentialoil of Cistus ladaniftrus L. atltiaated
compoundsthat were identified by W$'erstahl et al. can be ir"rCorsica (France). Flav. Fragr. 1., 12, I47 -151 (1997).
seen in F igure 2. N. Mrabet, S.Znra, M. M. Ismaili-Alaoui,H. Lahloaand B. Benjilali,
Essential oik ond resin gum from Moroccan Cistus, ''Ci.sttL.s
The acidsand lactonesthatwere determined in the acidic
ladaniferus L. Rivista Ital.-EPPbS. (Nurnero Speciale),622-630
fraction 60.27o\ were as follows: ,l r I 997).
hexanoicacid (O.7%) y-campholyticacid (0.2%) P.Weyerstahl,H. Marschall,M. Weirauch, K. Tliefeid and H. Surburg,
heptanoicacid(0.5%) camphonanicacid(2.4%) Corutituents of commerciallabdanuntoil. Flav. Fragr. J.. 13.295-
benzoicacid (0A%) octanoicacid (3.7%) 318 (1998).
291
Progress in Essential Oils
Reprinted
f romPerfumer
& Flavorist,
September/October
1999,Yol.24,No.5, P. 45
292
Using a combination of LC-GC/MS, Mondello et al. (Z)-B-ocimene (0.02%) citronellylacetate(0.05%)
(1994) fractionatedand characterizedthe presenceofmore 1-terpinene(4.12o/") neral (0.36%)
than 60 componentsof Italian bergamotoil. The compounds (E)-B-ocimene (0.14%) (Z)-B{arnesene(0.07%)
p-cymene(0.35%) o-terpineol+ o-terpinylacetate
identified were:
terpinolene (0.18%) ( 0 . 1 8 %)
tricyclene citronellol octanal(0.03%) y-muurolene (0.05%)
o(-thujene neral 6-methyl-3-heptanol nerylacetate(0.02%)
s-prnene crs-sabinene hydrateacetate ( <0 . 0 1 %) 2,7-dimeIhyl2,6-octadien-1-olt +
camphene linalylacetate nonanal(0.02/") B-bisabolene(1.43%)
sabinene geraniol octyl acetate(0.09%) 6-cadinene (0.33%)
B-pinene geranial decanal(0.04%) geranylacetate(0.24o/o)
myrcene bornylacetate linalool(16.27%) nerol(0.03%)
octanal undecanal linalylacetate(37.39%) geraniol(0.04%)
o,-phellandrene nonylacetate cr-bergamotene- (0.28%)
6-3-carene methylgeranate
o(-terpinene linalylpropionate " correct isomer not identified
hexylacetate o-terpinylacetate t tentativeidentification
(E)-B-ocimene dodecanal psoralens from bergamot oil. The authors compared the
T-terpinene usuyr ougLdLE compositionof two desorbedfractionstaken from the beein-
Irans-sabinene
hydrate c/s-s-bergamotene ning and end of isobaric desorption with the original oil
octanol B-caryophyllene and the residuesfrom the two fractions using GC/MS. The
terpinolene frans-0-bergamotene
results of these analysescan be seen in fabL I. As can be
linalool cr-humulene
nonanal (Z)-B{arnesene seen in Table I, the non-volatile compounds (such as the
heptylacetate B-santalene *T:r, coumarins and psoralens)were identified in the two
cis-limoneneoxide germacreneD res1oues.
frans-limoneneoxide germacreneB In 1996, Yerzera et al. used the previously reported
isopulegol B-bisabolene (Mondello et al. 1994)techniqueof LC-GC/MS io quantita-
camphor (Z)-ybisabolene
citronellal y-elemenst tively analyzebergamot oil and compare the analysei of over
terpinen-4-ol (E)-nerolidol 1,000 samplesof oil produced from the F antasticocultivar,
o-terpineol 2,3-dimenthyl-3-(4-methyl-3- 27 from the Castagnarocultivar and 1g from the Femminello
decanal pentyl)-2-norbornanol cultivar produced between 1g84 and 19g3. The composi-
octyl acetate campherenol
tional range of componentswas found to be as follows:
nerol s-bisabolol
tricyclene(0.002-0.007%) terpinolene(0.210-0.475y")
t incorrectidentitybased on elution order
othujene (0.190-0.491 %) frans-linalool oxide{uranoidl
This same year, Poiana et al. (1g94) described how ber- o-pinene(0.731- 1.844%) (0-t)
gapten could be partially removed from Italian bergamot camphene(0.022-0.053%) linalool(1.745-20 -260%)
sabinene(0.777-1.77B%) nonanal(0.012-0.0760/")
o i l by s uper c r it ic a l fl u i d (S C F C ) te c h n o l o g y . U si ng
B-pinene(4.374-11.024%) heptylacetate(t-0.008%)
8 mPa at temperaturesbetween 45oCand 50"C, the bergap- 6-methyl-5-hepten-2-one cis-limoneneoxide
ten content wasreduced fro m 0.3-0.47oto 0.05Va. Under the (0.0002-0.010%) (0.002-0.01e%)
above SCFC conditions the major compounds were found myrcene(0.656-1 .575%) frans-limonene oxide
to be: octanal(0.025-0.056%) (0.002-0.015%)
o-phellandrene isopulegol(01)
o(-thujene(0.3%) linalylacetate(26.4%) (0.025-0.056%) camphor (O.002-0.01 2o/o)
u-p ine ne(1.0 % ) nerylacetate(0.3%) hexylacetate(0-t) citronellal(0.004-0.030%)
sabinene+ B-pinene(8.8%) geranylacetate(0.8%) 6-3-carene (0.002-0.009%) terpinen-4-ol(0.013-0.042",t
myrcene(0.7%) lene (0.2%) "
B-caryophyl o-terpinene (0.081,0.282o/o) ct{erpineol(0.030-0.098%)
limonene(40.3o/o) lrans-cx,-bergamotene
(0.2%) p-cymene(0.060-0.893%) decanal(0.037-0.086%)
y-terpinene(8.3%) B-bisabolene (0.6%) limonene+ B-phellandrene octyl acetate(0.071-0.185%)
lin alo ol(1 1.1 % ) (25.626-53.187%) nerol+ citronellol
1,8-cineole (0.010-0.021 %) ( 0 . 0 1 0 - 0 . 1 1 1 %)
In 1995, Baseret al. examined an oil produced by labor- (Z)-B-ocimene neral (0.122-0.344%)
atory cold-pressing in the laboratory of Turkish-grown (0.017-0.068%) frans-sabi nene hydrateacetate
bergamotusing GC and GC/MS. The contponentsidentified (E)-B-ocimene (0.057-0.127%)
\\/ere: ( 0 . 1 0 4 - 0 . 3 6 1 %) linalylacetate(15.616-40.375%)
yterpinene(5.727-11-37B%) geraniol(0.004-0.01 0%)
u-pinene(0.81%) myrcene(O.78%) cis-sabinenehydrate geranial+ perillaldehyde
camphene(0.02%) p.07./")
o,-terpinehe (0.024-0.063%) (0.247-0.4940/")
hexanal(0.02%) limonene(32.28%) octanol(0.002-0.021o/o) bornylacetate(0.010-0.037%)
B-pinene(3.02%) B-phellandrene(0.15%) cis-linalooloxideJuranoidt undecanal(0.004-0.024%)
sabinene(0.55%) (E)-2-hexenal(<0.01%) (0-t) nonylacetate(0.004-0.053%)
293
Table lll. The effect of hydrodistillationat two different pH values on some chiral constituents of bergamot oil
ripeoil 31.7 68.3 9.4 90.6 98.3 1.7 98.7 1.3 62.6 37.4
Italianoil 1 32.0 68.0 8.6 91.4 98.4 LO 70.7 29.3 76.1 23.9
Italianoil2 30.8 69.2 8. 5 9 1. 5 95.1 4.9 100.0 0 48.6 51.4
lialianoil 3 30.2 69.8 8. 5 9 1. 5 98.1 1.9 77.7 22.3 62.0 38.0
Sicilianoil 31.2 68.8 8.3 91.7 98.2 1.8 68.6 31.4 76.7 23.3
Argentineanoil 37.0 63.0 8. 7 9 1. 3 98.7 1.3 100.0 0 36.0 64.0
Compoundedoil 29.3 70.7 5.2 94.8 98.7 1.3 64.2 35.8 63.5 36.5
Table V. Enantiomericdistribution of chiral compounds in authentic and commercial samples of bergamot oil
Brazil and Argentina, the majority of oil is produced becausethe (S)-enantiomerscould not have been produced
in Calabria. In 1997, Kcinig et al. discussedthe fact that by the processingconditionsusedto isolatethe bergamotoil,
limonene exists in authentic bergamot oil in the (R)-(*)- all of the commercial samples that they analyzed were
form, while linalool and linalyl acetateexist exclusivelyin the adulteratedto someextent;the degreeto which adulteration
(R)-(-)- form. The authors examinedth hexaneextractsof relates to the amount of (S)-enantio*erc found from the
freshly harvestedbergamot peels and determined that no addition of racemic linalool and linalyl acetateto the oil.
(S)-enantiomersof limonene, linalool orlinalyl acetatecould Dellacassaet al. (1997)comparedthe earlier quantitative
be found. Furthermore, Konig et al. determined that only 15 data on Italian bergamot oils (Verzeraet al. 1996)with the
of 52 purchasedsamplesof bergamot oil containedlessthan data obtained from the analysis of three Uruguayan oils
1.0% (S)-enantiomers.In all of these oils, (S)-linalool rvas produced by Sfumatrice.The range in compositionof these
accompaniedby(S)Jinalylacetate.The authorsnotedthat as three oils was determined to be as follows:
296
Table vl. The range of heterocycliccompounds (ppm) found in bergamot oil
produced by different isolation methods
Compound Sponge process (6)a Calabrese process (12) Pelatrice process (19)
bergamottin 7814-9123 8380-8822 6327-8263
5-geranyloxy-7-methoxycoumarin 555-923 529-869 534-1072
5-isopentenyloxy-7-methoxycoumarin 118-168 62-93 40_169
5-isopentenyloxy-7-methoxypsoralen 1-tz 0-8 u- t 3
citropten 2366-3566 1550-2616 1176-3207
bergapten 1548-2526 1711-3371 1893-3310
oxypeucedanin 172-261 343-392 180-475
byakangelicol 514-869 788-805 165-895
oxypeucedaninhydrate 65-83 46-54 22-59
byakangelicin 169-227 53-73 23-90
anumberof samplesanalyzed
tricyclene(0-0.003%) geraniol(t)
o-thujene (0.268-0.281 %) geranial+ perillaldehyde
O-pinene(1.077-1.137%) ( 0. 163- 0. 199% ) Table Vll. Enantiomericdistribution (%) of chiral
camphene(0.028-0.030%) bornylacetate(0.014-0.026%) compounds in a number of bergamot oil samples
sabinene+ B-pinene undecanal(0.011-0.017olo)
(6.552-6.879o/o) nonylacetate(0.021-0.026010)
myrcene(1.016-1.033%) Compound (R)-enantiomer (S)-enantiomer
methylgeranate(t-0.008%)
octanal(0.024-0.030%) linalylpropionate o-thujene (+) O-1.O (-) 99.0-100.0
cr-phellandrene (0.047-0.0620/0) cr-pinene (+) 26.3-38.4
(0.042-0.046%) e) d "6-75.7
6-elemene(1-O.002%) sabinene (+) 13.8-18.6 (-) 31.4-86.2
oterpinene (0.122-0.135"/.) c[{erpinylacetate (+) 6.3-8.6
B-pinene (-) 91.4-93.7
p-cymene(0.250-0.31 8%) (0.124-0.153%)
limonene+ B-phellandrene citronellylacetate(0.013-0.031%) limonene (+) 97.2-98.3 (-) 1.7-2.8
(38.135-42.545o/") nerylacetate(0.265-0.334%) linalool (-) 91.3-99.4 (+) 0.6-8.7
1,8-cineole (trace) geranylacetate(0.261-0.317%) linalylacetate (-) 99.7-99.8 (+) 0.2-0.3
(Z)-B-ocimene(0.024-0.028%) dodecanal(0.030-0.043%) citronellol (+) 80.0-88.0 (-) 12.0-20.0
(E)-B-ocimene (0.1B0-0.193%) decyl acetate(0.020-0.027%) cr-terpineol (+) 63.6-77.0 (-\ 2g.0-56.4
T-terpinene(6.190-6.485%) crs-o-bergamotene (t) o{erpinyl acetate (+) 56.0-6a.0 (-) 36.0-44.0
cls-sabinenehydrate B-caryophyllen e (0.344-0.SO2ok)
(0.019-0.020%) lrans-cI-bergamotene
octanol(0-0.003%) (0.s12-0.s87%) Using a 25 cm x 4.6 mm 10 pm sphericalsilicalcolumn run
terpinolene(0.256-0.27 3%) cr-humulene (O.047-0.070o/o)
linalool(8.908-9.521%)
at 25'C and gradientlyelutedwith hexane-ethylacetate(g:l)
(Z)-B{arnesene(0.040-0.068%)
nonanal(0.040-0.050%) (Z)-B-santalene (0.015-0.020%) to hexane-ethylalcohol (9:1), Gionfriddo et al. (199711998)
heptylacetate germacreneD (0.063-0.100%) successfullyachieved a HPLC analysisof the heterocyclic
(0.009-0.014%) bicyclogermacrene (0.37-0.53%) compoundsfound in bergamot oil. A summaryof the hetero-
(0.009-0.01
citronellal 0%) (E,E)-cr{arnesene (t)
terpinen-4-ol (0.018-0.021 ryclic compounds found in bergamot oil produced by three
%) B-bisabolene(0.431-0.556%)
uterpi neol (0.028-0.037./.)
different processescan be seen in Table VI.
(E)-nerolidol(0.13-0.26o/")
decanal(0.063-0.072%) tetradecanal(t) In 1998, Casiabiancaet al. carried out an enantiomeric
octylacetate(0.116-0.132%) 2,3-dimethyl-3-(4-methyl-3- study of the components of bergamot oil. Using chiral GC
nerol (0.024-0.0277o) pentenyl)-2-norbornanol on more than one column, the authors determined the
neral(0.109-0.126%) (0.012-0.023%) enantiomeric distribution of ten oil comDonentsas shown in
frans-sabinene hydrate camphenol(0.020-0.026%)
Table VlI.
acetate+ linalylacetate cr-bisabolol (0.019-0.031 %)
(28.853-31.835%) nootkalone(0.037-0.056%) In a recent report by Pudil et al. (1998)recently reported
on a GC/MS examination of the oxidative changesthat take
t = trace (< 0.00'1%) place in bergamot oil over the temperat.,." ,rrrg" of 40.-
Dellacassaet al. alsodeterminedthat the maior coumarins 60oC at restricted oxygenlevels.Although the authors did
and psoralens in the Uruguayan bergariiot oiis which were not present any true quantitative data, they did monitor the
as fbllows: FID peak areasof a number of compounds over the time
period of 0-739 h. The constituentsselectedfrom bergamot
bergamottin(1.655-1.749%)
oi l for moni l orj ngw ere.
5-geranoxy-7-methoxycoumarin (0.150-0.153%)
acelone (E)-B-ocimene
citropten(0.144-0.1460/0)
myrcene p-cymene
bergapten(0.111-0.112%) (Z)-B-ocimene cis-linalooloxide-
297
oils produced by different methods
Table vlll. comparative percentagecomposition of bergamot
1 2345 Compound
Compound
tricyclene 0.003 0.003 0.004 0.001 0.004 frans-sabinene
-
hydrateacetate 0.065 0.051 0 073 t
cr-thujene 0.281 0 .2 7 6 0 .3 2 0 0.119 0.318 8'880
1. 116 1.080 1.267 0.454 1.376 liniyl acetate 36.305 36.499 37 '644 22'757
o -pin en e
geraniol ttttt
camphene 0'032 0.033 0.035 0.016 0.048 t
0.001 0.006 0.009 t
sabinene+ B-Pinene8.154 7.963 8.815 4.238 7.921
i-decenal*
geraniol+
6-methyl-5-hePten- 0'281 0'118 0153
1 0.010 0.044 perillaldehyde 0.256 0922
2-one 0.050 0.013 0.01
0.014 0.019 0 015 0'022 0'160
myrcene I
0.813 0.791 0.832 0.713 1"31 bornylacetate
0.004 0'003 0 oOG 0'002 0'010
octanal 0.030 0.039 0.048 0.019 0.180 indole
0'020
undecanal 0.009 0.010 0 012 0'010
o-phellandrene 0.026 0.023 0.024
I furanoidform
* correctisomernot identified
t = trace (< 0.001%)
1 = Torchiatioils 'r
2 = Riciclioils
3 = Puliziadischioils
4 = Distilledoil - reducedpressure
5 = Distilledoil - atmosphencpressure
298
frans-linalool
oxide* y-terpineol
dihydrolinalool Table lX. Enantiomericdistribution (%) of
some components of cold-pressedbergamot oil
* correct isomer
not identiJied (101sampl es)
Becausethe choice of the abovecompoundsis not ideal,
Compound (R) (S)
the value of this study is minimal.
Verzeraet al. (1998) compared the analysesof bergamot B-pinene (+)6.8-9.5 (-) 90.5-93.2
oil produced by different processingmethods. Using GC/ sabinene (+) 14.1-18.8 (-) 81.2-85.9
limonene (+) 97.3-98.1 (-) 1.9-2.7
MS and retention indices as their method of comoonent
linalool (-) 99.4-99.7 (+) 0.3-0.6
characterization,the authorsdetermined the compositionof
three oil tlpes recoveredby cold treatments(Ricicli,Torchiati terpinen-4-ol (-) 73.7-90.3 (+) 9.7-26.3
c{,-terpineol (+) 30.6-82.5 (-) 17.5-69.4
and Pulizia dlschi) and two oils produced by distillation linalylacetate (-) 99.7-99.9 (+) 0.1-0.3
(atmospheric and reduced pressure).The results of these
analysesare found in Table VIIL The same authors also
reportedthe resultsof more than 1,500analysesof bergamot
oil produced over the 1984-1997time period. A summary Table X. Enantiomericdistribution (%) of
of these results is as follows: some components in "Torchiati", "Ricicli"
and " P ul i zi aD i schi di schi "bergamotoils
tricyclene(0.001-0.005%) carvone(01)
crthujene(0.187-0.4917") frans-sabinene hydrate acetate "Torchiati" "Ricicli" "Puliziadischi" Cold-pressed
o-pinene(0.720- 1.844%) (0.048-0.127%) Compound gf @ (3) (29)
camphene(0.019-0.053%) linalylacetate(15.616-41 .363%)
B-pinene+ sabinene geraniol(0-0.010%) B-pinene
(4.814-12.802%) 2-decenal*(0-0.009%) R (+) 7.86-8.5 7.4-7.9 7.8-8.0 7 .1- 9 .0
6-methyl-5-heplen-2-one geranial+ perillaldehyde s (*) 91.5-92.4 92.1-92.6 92.0-92.2 9 1 .0 - 9 2 .9
(0.001-0.009%) (0.199-0.494olo) sabinene
myrcene(0.635-1 .575%) bornylacetate(0.010-0.037%) R (+) 14.7-15.01 4 . 5 - 51 . 0 14.7-15.0 1 4 .1 - 1 8 .8
octanal(0.025-0.084%) indole(0-0.009%) s (-) 85.0-85.3 85.0-85.5 85.0-85.3 8 1 .2 - 8 5 .9
o-phellandrene undecanal(0.004-0.024%) l l monene
(0.016-0.056%) nonylacetate(0.004-0.053%) s (-) 2.1-2.3 2.2-2.3 2.21-2.32 2.O-2.6
hexylacetate(0-0.002%) methylgeranate(0.002-0.01 5%) R (+) 97.7-97.9 97.7-97.8 97.8-97.9 97.4-98.0
6-3-carene (0.001-0.009%) linalylpropionate linalool
cr-terpinene (0.081-0.282%) (0.013-0.066%) R (-) ee.6 99.5-99.6 99.5-99.6 99.4-99.6
p-cymene(0.010-0.893%) 6-elemene(0-0.O07%) S (+) 0.4 0.4-0.5 0.4-0.5 0.4-0.6
limonene+ B-phellandrene o,-terpinyl acetate terpinen-4-ol
(25.385-53.187%) (0.071-o.263%) S ( +) 1 8 . 1 - 1 9 . 1 18.7-21.4 IZ- J- I J. I 9.7-20.0
1,8-cineole(0.010-0.022%) citronellylacetate R (-) B0.e-81.e 78.6-81 .3 86.9-87.7 80.0-90.3
(Z)-B-ocimene (0"011-0.068%) (0.007-0.053%) a-terpineol
(E)-B-ocimene (0.104- nerylacetate(0.126-0.670'/") s (-) 4.s-10.5 6 . 4 - 1 8 . 7 27.5-41.8 20.7-44.1
0 .36 1% ) geranylacetate(0.107-0.799o/o) R (+) 8e.5-95.1 8 1. 3 - 9 3 . 6 58.2-72.5 55.9-79.3
^y-terpinene (5.266-1 1.151%) dodecanal(0.002-0.055%) linalylacetate
cls-sabinenehydrate decyl acetate(0.009-0.053%) R (-) ee.7-ee.e99.7-99.8 99.7-99.8 99.8-99.9
(0.015-0.063%) cis-c)[-bergamotene S ( +) 0.1-0.3 0.2-0.3 0.2-0.3 0 .1 - 0 .2
octanol(0.001-0.021%) (0.017-0.048%) * number
of samples
cls-linalooloxidet (01) B-caryophyllene
terpinolene(O.21 0 -0.476%) (0.154-0.524%)
trans-linalool oxidet (0-t) frans-cr-bergamotene campherenol(0.007-0.023%) nootkatone(0.010-0.095%)
linalool(1.745-22.681%) (0.162-0.437o/o) s-bisabolol(0.007-0.030%)
nonanal(0.012-0.076%) o,-humulene (0.009-0.045'l.)
heptylacetate(t-0.019%) (Z)-B{arnesene(0.033-0.089%) f furanoid form
* correct
isomer not identilied
cis-limoneneoxide (Z)-B-santalene (0.001-0.016%) t = tr ac e {< 0.001% )
(0 .00 1-0 .01 9%) dodecanol(0-0.009'/")
trans-limonene oxide germacreneD (0.033-0.1 06%) This sameyear,Mondello et al. (I998a) describedin detail
(0 .00 1-0 .01 5%) bicyclogermacrene the use of multidimensional HPLC-GC/MS and GC/GC/
isopulegol (0-0.004%) (0.012-0.076%) MS to analyzebergamot oil. The paper describedthe tech-
camphor(0.001-0.012%) (Z)-cr-bisabolene(01)
citronellal(0.005-0.030%) (E,E)-a-farnesene (01)
nicues used in detail.
terpinen-4-ol (0.008-0.042%) B-bisabolene(0.212-0.6480/) \,Vithth" ,,,r"of chiral GC analysis,Mondello et al. (1998b)
"
o{erpineol(0.030-0. 126%) (Z)-ybisabolene (0-0.010%) examinedthe enantiomericdistribution of a few constituents
dodecane(0-0.006%) germaiieneB (0-0.001 0%) of bergamot oil. A sumrnaryof these results can be seen in
decanal(0.037-0. 103%) (E)-nerolidol(0.007-0.036%) Table IX. The authorsalso examinedthe effect of bergamot
octyl acetate(0.071-0.199%) tetradecanal(0-0.010%)
nerol+ citronellol
oil isolation by diff'erent processeson the enantiomedc
2,3-dimethyl-3-(4'methyl-3-
(0 .01 0-0 .11 1%) pentenyl)-2-norbornanol distribution of these same comDounds:theresults of rvhich
neral(0.105-0.344%) (0.006-0.024%) are shown in Table X. F inally, enlntiomeric distributions of
299
M. Poiana, E. Reverchon,V. Sicari, B. Mincione and F. Crispo,
Table Xl. Enantiomericdistribution (%) of some
Supercritical corbon dioxid,eertraction ofb ergamot oil : b ergapten
components of distilled bergamot oils and some Bergapten content in the extracfs. Ital. j. Food Sci., (4), 459-466
bergapten-freeoils (1994).
K. H. C. Baser,T. Ozek and M. Tutas,Compositionof cold-pressed
Distilled oils Bergapten-free oils bergam,otoilfromTurkeq. J. Essent.Oil Res.,7,341-342 (1995).
Atmospheric Reduced NaOH Distilled
D. Chouchi,D. Bafth, E. ReverchonandG.DellaPofta,Supercritical
Compound pressure treated
CO2 de,so:tion ofbergamotoil. Ind. Eng. Chem. Res.,34, 4508-
B-pinene 4513(1ee5).
R (+) 8.9 8.2 8.2-8.7 8.1-9.2 A. Verzera,G. Lamonica,L. Mondello, A.'frozzi and G. Dugo, The
s (-) e 1 .1 91.8 91.3-9r.8 90.8-91.9 composition of bergamot oil. Perfurn. Flavor., 2f (6), 19-34
(1ee6).
sabinene
R (*) r5.9 B. D. Baigrie, M. G. Chisholm and D. S. Mottram, The ffict of
I5.2 15.3-15.7 15.1-16.0
s (-) 84.1 84.8 84.3-84.7 84.0-84.9 ltrocessingon chiral oroma compoundsinfntits ond essentialoils.
In: Flaoour Science:Recent Deuelopments. Edits., A. J. Taylor
limonene and D. S. Mottram, pp. 152-157, Royal Institute Chem.,
s (-) 2.0 2.3 2.r 2.1.-2.2 Cambridge (1996).
R (*) e8.0 v l.l 97.9 97.8-97.9 M. Calvarano, E. Postorino, F. Gionfriddo, L Calvarano and F.
linalool Bovalo, Naringin extraction from exhausted bergamot peels.
R (-) 8r.6 9 8 .7 99.6 99.5-99.6 Perfum. Flavor., 2f (5), 1-4 (1996).
S( * ) 18.4 l.r) 0.4 0.4-0.5 D. Juchelka and A. MosandI, Authenticity profi,le,sof bergamat oil.
terpinen-4-ol Pharmazie, 51, 417-422 (1996).
S (*) 31.8 27.r 18.4-20.1 19.8-21.5 W. A. Konig, C. Fricke, Y. Saritas,B. Momeni and G. Hohenfeld,
Adulteration or nntural aariabilitq'P Enantioselectioe gas
R (-) 68.2 72.9 79.9-81.6 78.5-80.2
chromotography in purity cctntrol of essentialoil,s.I. High Resol.
o-terpineol Chromatogr.,20, 55-61 (1997).
s (-) 26.6 rr.2 3r.4-52.r 1r.4-50.5 E. Dellacassa,D. Lorenzo, P. Molaia, A. Verzera and A. Cavazza,
R (*) 7s.4 88.8 47.9-68.6 4e.5-58.6 Uruguayan essentialoi,ls.Paft V. Composition of bergamot oil.
linalyl acetate J. trssent.Oii Res.,9,4f9-426 (f997).
R (-) 9 8 .9 99.1 99.7-99.8 99.7-99.9 F. Gionfriddo, E. Postorino and F. Bovalo, On atthenticity of
s (* ) 1 .1 0.9 0,2-0.3 0.1-0.3 bergamot oil: HPLC profiles ofheterocyclic corrytonents.Essenze
Deriv. Agrum., 67, 349-352 (1997); Rivista ltal., (Numero
Speciale),96-104 (1998).
components in distilled and bergapten-free oils were also H. Casabianca,M. C. B ertrand and C. C r enier, Enanti omeric stud4
examined (and are shown in Table XI). of bergannt oils. RivistaItal., EPPOS, (Numero Speciale),45-58
( 1998).
A. Mosandl, U. Hener, P. Kreis and H. G. Schmarr,Enantiomeric
P. Pudil, j. Volfova, V. Janda,H. Valentova andJ.Pokorry,Effect of
distribution of ct-Pinenepinene,ftPinene pinene and Limonene
rosemory and l,4-dihyclropyridines on oxidatiae and flauor
limonene in essential oils and extracts. Paft I. Rutaceae and
changes in bergamot oil. Irr: Food Flauors: formntion, analysis
Graminae.Flav. Fragr. J., 5, 193-199(1990).
and packaging influences.Edlts., E. T. Contis, C-T. Ho, C. J.
A. Mosandl and V. Schubert, StereoisomereAromastoffe )L{XIX Mussinan,T. H. Parliament,F. Shahidi and A. M. Spanier,pp.
Chirale lnhaltstffi iitherischer Ole L stereodffirenzierung 679-868,EIsevier,Amsterdam (1998).
des linalyl-rrcetats Ein neuer Weg zur Qualitritsbeufteilung des
A. Verzera,A. Trozz|l. Stagno-D'Alcontres,L. Mondello, G. Dugo
Lanandeli;k.Z. Lebensmitt.Unters.Forsch.,f 90,506-510(1990).
and E. Sebastiani, The composition of the aolatile fraction of
M. Benincasa,F. Buiarelli, G. P. Cartoni and F. CoccioIi,Analqsis Calabrian bergamat es,sentialoil. Rivista Ital., EPPOS, (25),
of lennn andbergamot essentiol oils by HPLC uith microbore 17-38(1998).
col,umns.Chromato grapia, 3O, 271 -276 (1990).
L. Mondello, P. Dugo, A. Cotroneo,A. R. Proteggenteand G. Dugo,
H. Casabianca and J-B. Graff, Separation of linalyl acetate Multidimensional adoanced techniques for the ana.lysis of
enantiomers:Aytplication to the authentication of bergamatfood bergamat oil. Rivista Ital., EPPOS, (26),3-27 (1998a).
j. High Res.Chromatog.,l7,184-186(1994).
1:roducts. L. Mondello, A. Verzera, P. Previti, F. Crispo and G. Dugo,
G. Ohloff, Scentanclfragrances. Thefascinationof odors andtheir Multidimensional capillarq CC-GC for the analysis of
cltemical p erspecti,Des.Translated by W. Pickenhagen and B. M. complexsomples.5. Enantiomeric clistribution of m,onotewene
Lawrence, pp. 129-130, 138-139, Springer Verlag, Berlin, hydrocarbons, monotery)ene alcohols and linalyl acetate of
Heidelberg(1994). bergamnt (Citru,s bergamia Rissoet Poitem,) oils. J. Agric. Food
L. Mondello, K. D. Bartle,P. Dugo, P. GansandG. Dugo,Aaromnted Chem., 46, 4275-4282(1998b).
LC-GC: Apouetful methodfor cssey[ioloils analaysis.Paft IV.
CoupledLC -GC -MS( ITD) fttrbe rgamntoil analysis.J. Microcol.
Sep.,6, 2s7-214 (1994).
A. Bemreuther and P. Schreier, Multklimensional gas chromato-
graphy /mass spectrometry: A powbtful tool for the direct chiral
eaaluation of aroma compounds in,plant tiswes. IL L linalool in
essential oilsandfruits. Phltochem. analysisAnalysis,2, 167-170
( 1991).
300
M. Poiana, E. Reverchon,V. Sicari, B. Mincione and F. Crispo,
Table Xl. Enantiomericdistribution (%) of some
Supercritical carbon dioxide extraction ofb ergamot o il : bergapi en
components of distilled bergamot oils and some Bergapten content in the extracts. Ital. J. Food Sci., (4), 459-466
bergapten-free oils (1ee4).
K. H. C. Baser, T. Ozek and M. Tutas, Comytositionof cold-pressed
Distilledoils Bergapten-freeoils b ergamot oil from Turkey. J. tr ssent.Oil Res., 7, 34L-342 (1995).
Atmospheric Reduced NaOH Distilled D. Chouchi, D. Barth, E. ReverchonandG. DellaPorta, Sr;percritical
Compound pressure treated
C02 desorptionofbergamatoil. Ind. Eng. Chem. Res.,34,4508-
F-pinene 4513 (1995).
R (*) 8.9 8.2 8.2-8.7 8.1-9.2 A. Verzera,G. Lamonica,L. Mondello, A. Trozzi and G.Dlgo,The
s (-) e 1 .1 91.8 91.3-91.8 90.8-91.9 comltosition of bergamnt oil. Perfum. Flavor., 2f(6), 19-34
(1996).
sabinene
R (+) B. D. Baigrie, M. G. Chisholm and D. S. Mottram,The ffict of
1 5 .9 L5.2 15.3-15.7 15.1-16.0
processingon chiral aroma compoundsinfruits and essential oils.
s (-) 84.r 84.8 84.3-84.7 84.0-84.9 In: Flauour Science:Recent Deaelopments. Edits., A. J. Taylor
Iimonene and D. S. Mottram, pp. 152-157, Royal Institute Chem.,
s (-) 2.0 2.3 2.t 2.1-2.2 Cambridge (1996).
R (+) 98.0 Y l.l 97.9 97.8-97.9 M. Calvarano, E. Postorino, F. Giontriddo, I. Calvarano and F.
linalool Bovalo, Naringin extraction from exhausted bergamot peels.
R (-) 81.6 98.7 99.6 99.5,99.6 Perfum. Flavor., 2f (5), 1-4 (1996).
S (*) 18.4 l.t) 0.4 0.4-0.5 D. Juchelka and A. Mosandl, Authenticittl profiles of bergamot oil.
terpinen-4-ol Pharmazie, 51, 417-422 (1996).
S (*) 31.8 27.r 18.4-20.119.8-21.5 W. A. Konig, C. Fricke, Y. Saritas,B. Momeni and G. Hohenfeld,
Adulteration or natural uariabilitg? Enontioselectiae gas
R (-) 68.2 72.9 79.9-81.678.5-80.2 chromatography Resol.
inpurity control of essential oils.l. High
u-terpineol Chromatogr.,20, 55-61 (1997).
s (-) 26.6 rr.2 37.4-52.1 1r.4-50.5 E. Dellacassa,D. Lorenzo, P. Moyra, A. Verzera and A. Cavazza,
R (*) 73.4 8 8 .8 4 7 .9 -6 8 .6 49.5-58.6 Uruguayan essentialoils. Par-tV. Composition of bergam.otoil.
linalyl acetate J. Essent.Oil Res.,9,419-426 (1997).
R (*) e8.e 9 9 .1 9 9 .7 -9 9 .8 99.7-99.9 F. Gionlriddo, E. Postorino and F. Bovalo, On authenticity of
S (+) 1.1 0 .9 0 .2 -0 .3 0.1-0.3 bergamnt oil : H PLC profi,lesofhet erocyclic component,s.Essertze
Deriv. Agrum., 67, 349-352 (1997); Rivista Ital., (Numero
Speciale),96-104 (1998).
components in distilled and bergapten-free oils were also H. Casabianca,M. C. Bertrand and C. Grenier,Enantiomeric,studq
examined (and are shown in Table XI). ofbergamntolls. RMsta Ital., trPPOS,(Numero Speciale).a5-58
(1998).
A. Mosandl, U. Hener, P. Kreis and H. G. Schmarr,Enantiomeric
P. Pudil, J. Volfova, V. janda, H. Valentova and j. Pokorny, Effect of
distribution of a-Pinenepinene, PPinene pinene and Limonene
rosemary and l,4-dihydropgridines on oxidatioe and flaaor
litnonene in essential oils and extracts. Part L Rutaceae and
changes in bergamat oil. In: Food Flaaors: formation, analysis
Graminae. Flav. Fragr. J., 5, 193-199(f990).
andpackaginginfluences. Ediis., tr. T. Contis, C-T. Ho, C. j.
A. Mosandl and V. Schubert, StereoisomereAromastoffe )tLVX. Mussinan,T. H. Parliament,F. Shahldi and A. M. Spanier,pp.
Chirale inhaltstffi titherischer Ole I. Stereodiffi ren zieru ng 679-868,Elsevier,Amsterdam (1998).
des linalgl-acetats Ein neuer Weg zur Qualitritsbeufteilung des
A. Verzera,A. Trozzi,I. Stagno-D'Alcontres,L. Mondello, G. Dugo
Laa andelrjls.Z. Lebensmitt. Unters. Forsch.,190, 506-510 (1990).
and E. Sebastia.'i, The composition of the aolati,lefraction of
M. Benincasa,F. Buiarelli, G. P. Cartoni and F. Coccioli, Analysis Calabrian bergamnt essential oil. Rivista Ital., EPPOS, (25),
of leman and bergamot essential oils by HPLC uith microbore 17-38(1998).
columns.Chromatograpia, 3O,27l-276 ( 1990).
L. Mondello, P. Dugo, A. Cotroneo,A. R. Proteggenteand G. Dugo,
H. Casabianca and J-8. Graff, Separation of linalyl a.cetate Multidimensional adoanced techniques for the analysis of
enantiomers:Application to the authentication of bergamatfood bergamotoil. Rivista Ita]., EPPOS, (26),3-27 (1998a).
products.J. High Res.Chromatog.,17,184-186(1994).
L. Mondello, A. Yerzera, P. Previti, F. Crispo and G. Dugo,
G. Ohloff, Scentandfragrances. Thefascination of odors and their Multidimensional capillary GC-GC for the analysis of
chentical perspectiDes.Translated by W. Pickenhagen and B. M. complex samples. 5. Enantiomeric distribution of monoterene
Lawrence, pp. 129-130, 138-139, Springer Verlag, Berlin, hydrocarbons, monoterTene alcohols and linalyl acetate of
Heidelberg (1994). bergamot (Citrus bergamia Rissoet Poitem) olls. J. Agric. Food
L. Mondello,K. D. Bartle,P. Dugo, P. GansandC.Du.go,Automated Chem., 46, 4275-4282(1998b).
LC-CC: A pouerful methodfor essentig!oils analaysis. Paft IV.
CoupledLC -CC -MS(ITD) forbe rgambtoil arialysis.J. Microcol.
Sep.,6, 237-214 (L994).
A. Bernreuther and P. Schreier, Multirlimensional gas chromato-
graphy/mass spectromelnj:A powetful loolfor tie direa chirol
ersaluationof aroma compounds in plant tissues.IL L linalool in
essential oilsandfruits. Phyochem. analysisAnalysis,2, 167-170
(199r).
300
FeverfewOil and Extract
B{arnesene* bornylacetate
Tlre herb Tanacetumparthenium(L.) Schultz_Bip.which is germacrene
D bornylangelate
a perennial member of the Asteraceaefamily. is gaining trans-chrysanthenyl
acetate 8 spiroketalenolethers(1-B)l1l_t8l
cis-chrysanthenol costunolide(9)[9]
popularity because of its reputed migraine propiylactii c/s-chrysanthenylacetate 3B_hydroxycostunolide(10)1101
qualities (Hobbs 1989, Awang 19gg). Recentty, ,t"ay Uy crs-chrysanthenyl
angelate reynosin(11)t11l
"
Palevitchet al. ( 1997)(cited in Awang 1998) determined cis-chrysanthenyl
isovalerate parthenolide(12)1121
that
air-dried feverfew leaves could be used prophylactically to crs-verbenol 3B-hydroxyparthenolide (13)t131
reduce the pain intensity of migraine anj its side effects. It 4-acetoxychrysanthenone methylcostate(14)t141
was pointed out by Awang that the probable active principle An^oil of Belgium Belgian T. pat-theniu?rl was analyzed,
,
of T.pafthenir,rmwasthe sesquiterpenelactone paftfrerroli'd", by GC and GC/MS by Dlpooter et al. (1989) and found
which has been found to occur at levels of approximately to contain:
0,2-0.77o.However, Awang further stated thif other con_ cr-thujene(0.6%) borneol(1.0%)
stituents could also be biologically active and may, along crc-pinene(1.0%) pinocarvone(t)
alone or together with parthenolide, be responsiblefor thJ camphene(5.4%) terpinen-4-ol(2.8%)
sabinene(t) frans-chrysanthenylacetate
migraine prophylaris.
B-pinene(t) (23.5%)
The reason for this review is that oils and extracts of cx,-phellandrene(0.6%) bornylacetate(0.7%)
T,pafthenium have startedto appearin commerce.In lgg2, p-cymene(3.1%) eugenol(t)
Bohlmann and Zdero analyzed-adiethyl ether/petroleum limonene(0.5%) (t)
B-caryophyllene
y-terpinene (1.0%)
extract of T. patthenium. After the extract was treated with B{arnesene.(0.8%)
linalool(1.3%) germacrene D (4.6%)
methanolto removethe long long-chainhydrocarbons,itwas
camphor(44.2%) 6-cadinene(t)
fractionatedover silica gel using gradieni elution. The vola_
"correct isomer not identified
tile compouncls identifild in this"extract were: t = tr ac e ( < 0.1% )
Me(c=c)2-g{0,,,* Me(c=c)2-X{O,,,,*
1 R=H 4 R=H
2 R=OAc R = OA c
l'R = OisoVal o R = OisoVal
Me(c=c),_"{(])
7 cis
8 trans q F l - tl
10 R = OH
C O2Me
/+O
12 R=H
-
13 R=OH
14
Figure1' selectedvolatilecompouhdsfrom diethylether/petoleum
extractot r. parthenium.1-g=spiroketalenol
ethers,9=costunolide,10=3F-hydroxycostunolide,tt=rbynosin,iz=partnenoiio",rC--lp-hydroxparthenolide,
14 = rns1ftylcostate
301
The followingyear,Banthorpeet al. (1990)usedGC, GC/
TableXll. Percentage
compositionof
MS, HPLC and ]H-NMR to examinea diethyl ether extract Tanacetum partheni um oils
of the flower heads of T. paftheni.unr,.The following com-
oounds that were identified in the flower head extract were: Compound 1 2
2- methy12,4-pentadiene* stigmasterol(t) o-thujene 0.70 I
(0.2"/.) B-sitosterol(2.6%) benzaldehyde t
0,-thujene(0.2%) eugenol( 0. 1% ) o-pinene 1.65 o.25
cr-pinene(0.2%) caryophylleneoxide (0.4%) camphene 6.46 1 .5 9
camphene(0.7%) hexanal(t)
sabinene 0.33
B-pinene+ sabinene(0.2%) (E)-2-hexenal (t)
myrcene(t) camphor(18.9%) p-pinene 0.27 0 .1 1
6-3-carene(t) pinocarvone(0.2%) c{,terpinene 2"98 1 .0 9
p-cymene(0.5%) isoamylisovalerate(0.2%) p-cymene 0.63 0 .2 1
butylbenzenet (i) ethyloctanoate(0.1%) limonene t i
lterpinene (0.1%) frans-chrysanthenylacetate 1,8-cineole t t
p-cymene(t) ( 15. 5% ) p-methylbenzaldehyde t t
B-caryophyllene (T) bornylacetate(0.7%) yterpinene 1.87 o .1 7
cr{arnesene*(t) benzyl2-methylbutyrate
3-docosene.(6.0%) (0.5%) sabrnenehydrate- 0.10
(Z)-3-hexenol(t) dehydrosassaurea lactonet p-cymenene t t
benzylalcohol(t) (0.6%) terpinolene t 0.22
sabinenehydrate.(t) parthenolide(28.4%) trans-chrysanthenol 1.42
borneol+ sabinol.+ terpinen- spiroketal enolethers(6.5%) camphor 42.73 6 1 .8 0
4-ol (0.4%) pinocarvone O.14 0.22
borneol 0.60 0.59
t tentative identification
* correct isomer not identified p-ethylbenzaldehyde t
t = trace (< 0. 1%)
terpinen-4-ol 0.27 0.54
In comparison, the major leaf volatiles were: o-terpineol 0.17 I
cuminaldehyde t
camphene(3.0%) (1.6%)
B-sitosterol frans-chrysanthenyl 1 3 .8 3
acetate 24.00
camphor(2O.1%) C24 hydrocarbon (25.0%)
trans-chrysanthenyl
acetate C26 hydrocarbon(14"0%) benzylpropionate t
A.7o/ol bornylacetate 1.90 i nu
germacreneD (3.1%) benzylisobutyrate t I
parthenolide
(6.1%) thymol t I
carvacrol t
According to Heptinstall et al. (1992), parthenolide is
propjonate
trans-chrysanthenyl t t
found in high levels in the leaves, flowering tops and seeds of linalylpropionate t
T, parthenolide and in low levels in the stems and roots. Two thujopsene 0.10
years later, Smith and Burford (1994) analyzed a CO,
benzylisovalerate t 0. 10
supercritical fluid extract ol T. pafthenium :using GC/MS. cx,-copaene t 1
They found that it contained: B-caryophyllene 0.53 0 .2 1
cr-humulene t I
o-pinene(0.4%) bornylacetate(0.8olo)
camp he ne(2 .1% ) (1.0%)
dihydroparthenolide B{arnesene* 2.52 I
camphor(20.9'/") parthenolide
(17.9%) curcumene' t I
borneol(0.4%) trans-chrysanthenyl
isovalerate t I
chrysanthenylacetate" germacrene D 3.03 t
(10.4%)
6-cadinene t I
" correct isomer not identified frans-chrysanthenyl
angelate t I
caryophyllene
oxide 2.06 1 .0 2
In 1996, Hendriks et al. analyzeda lab-distilled oil pro- C13-compoundt 0.84 0 .1 0
duced from both fresh and dried T. pafthenium using GC C14-compoundt t
and GC/MS. The comparativecompositionof these oils can " .**"t ir"rn"|. identified
be seenin Table XII. They alsomonitored the changesin oil i spiroketal ""t
etherpolyines
composition during the maturing of plants grown in the t = trace(< 0.1%)
1 = oilfromfreshherbage;2 = oilfromdriedherbage
Netherlands.These results are showp*inTable XIII.
Finally, Hendriks et al. (1996) recommended that a true
oil of Z parthenium should contain camphor (>257o),trans- the reasons why the severity of migraines is purported to be
chrysanthenylacetate(>107o)and q*-and B-thujone (trace- reduced with the use of I parthenium.
0.I7o). The authors also noted that the presence of
F. Bohlmann and C. Zdero, Sesquiterpenelactones and other
trans-chrysanthenylacetatewasimportantbecauseit is known constituentsfrom Tanacetum parthenium. Phytochemistry,21,
to inhibit prostaglandinsynthetase,which could be one of 2543-2549 (1982).
302
Laurel Leaf Oil
TableXlll.The percentagecompositionof
Tanacetumpartheniumoil producedfrom plants In 1967, Kekelidze compared the composition of leaf oils
harvestedat variousdevelopmentalstages versus stem oils of Launts nobilis grown in the former Soviet
Union. The results of this comparison are shown in Table
Compound Stage 1 Stage 2 Stage 3 XIV As can be seen,the oils were found to be verv similar.
othujene 0.34 0.40 0.37 Fouryearslater,Pruidze et al. (1971)determined that leaf
cr,-ptnene 1. 99 1. 65 2.42 storage had little effect on the oil composition of laurel leaf.
camphene 6.42 7.74 7.44 In 1977, Kekelidze et al. used GC to examinecompare the
sabinene 0.33 0.34 0.25 composition of the fruit oil and leaf oil of L. nobilis (which
B-pinene 0.22 0.28 0.34 they compared to the leaf oil as shown in Table XV).
ct-terpinene 3.84 2. 19 2.57 In 1985, Kekelidze showed that leaf dryrg had little
p-cymene 0.72 0.74 0.63
y-terpinene effect on the quantitative composition of laurel leaf oil. Two
2. 71 2.67 1.49
yearslater, this sameauthor (Kekelidze 1g87)comparedthe
sabinenehydrate- 0.03 0.03 compositionof the wood, leaf and stem oils of.L. nobilis.'the
trans-chrysanthenol 2.06 1 .6 9 1 .31
campnor 28.00 32.50 43.20 results of this study are shown in Table XVI. To determine
prnocarvone o.02 0.04 0.0s
borneol 0.66 1 .1 4 1 .10 Table XlV. Comparativepercentagecomposition
terpinen-4-ol 0.49 0.57 0.82 of leaf oil and stem oil ol Laurus nobilis
0-terpineol o. 12 0 .1 1 0 .14
trans-chrysanthenyl
acetate 30.20 26.00 22.90 Compound Leaf oil Stem oil
bornylacetate t.ol 1. 87 1. 7 0 0-prnene z.z-J.I 2.5-4.3
thujopsene 0. 11 0.08 0.24 campnene 0.5-0.6 0.4-0.5
B-caryophyllene 0. 41 0.39 o.29 B-pinene 3.8-4.5 2"9-4.1
B-farnesene* 2.98 2. 63 1.2 4 sabinene 5.5-6.0 5.9-6.3
germacreneD 0.66 1. 26 0.89 myrcene 2.2-3.0 z - u -z -3
caryophylleneoxide 2.04 2. 01 0.95 cr-phellandrene 0.7-0.8 0.4-0.6
oil yield(%) 0.53 0.43 0.83 limonene 1.6-2.2 2.0-2.6
B-phellandrene 0.7-0"8 0.5-0.6
' correctisomernot identified
1,8-cineole 33.9-36.6 32.9-35.1
Stage 1. = rosettestage
p-cymene 0.8-1
.0
Stage2. = bud formation t.o-2.+
303
AIso in 1987, Kekelidze et al. (1987b) examined the
Table XVl. Comparativepercentagecomposition of
the stem, bark and wood oils ol Laurus nobilis changesin the major constituents of the oil of young and
adult L. nobilis leavesover a l4-month oeriod. The resultsof
Compound Stemoil Bark oil Wood oil this study are fbund in Table XVII. As can be seen, oil
produced from leaves harvested betr,veenApril and July
a,-pinene 3 .5 4. 0 1 .0
show the widest range in compositional difference of oil
0.2 0. 3 < 0.1
B-pinene 3 .6 4. 3 0.3 produced either from young or mature leaves.As a result,the
sabrnene 8 .7 7. 6 tc.J authors recommended that, because of seasonal
myrcene 0 .8 1. 0
climate changes,L. nobilis should be harvestedfor oil pro-
0.2
o,-phellandrene 0 .1 0.2 <0.1 duction from September/Octoberthrough Febmary
limonene t.3 1. 8 <0.1 In 1990, Kreis et al. used enantiomeric separation on
B-phellandrene 0 .4 0. 6 <0.1 a chiral capillary GC column to determine that the enan-
1,8-cineole 32.8 37.7 7.9 tiomeric ratios of cr-pinene, B-pinene and limonene in
y-terpinene 0 .2 0. 3 <0.1 L. nobili,soil was found to be were,
p-cymene 0 .4 0. 5 <0.1
terpinolene 0 .1 0. 2 <0.1 (S)-(-)-cr-pinene
(39%): (R)-(+)-cr-pinene
(61%)
(S)-(--)-B-pi
nene (44'/"): (R)-(+)-B-pinene
(56%)
linalool 6 .6 6. 6 6.2
terpinen-4-ol 7.0 6. 8 8.4
(S)-(-)-limonene
(<1%): (R)-(+)-limonene(>99%)
B-caryophyllene 0 .4 0. 7 0.7 Three samplesof laurel leaf oil were subjectedto analysis
0-terpineol 0. 3 1.9
byonline-coupled GC/MS with chiral GC (Bernreuther and
crterpinylacetate 20.5 17. 3 44.8 Schreier 1991). The authors found that the enantiomeric
methyleugenol J.Z J. l 3.8
distribution of linalool was R-(-)-hnalool (55.3-77.2Vo):
eugenol 2 .2 1. 7 5.0
S- ( + )Jinalool (22.8-44.7Eo).
In 1992,Appendino et al. extracted L. nobilis fiuits with
CHCI". A{ter successiveextractionwith methanol and frac-
tionation through a silicagel column using gradient elution,
what the oil losseswere during laurel leaf oil production, the
they identified l2-acetorygermacra-1( 10),5-dien-4,1 l-diol
water water-soluble oil components were determined
and some sesquiterpenelactones in one of the fractions.
chromatogaphicallyby Kekelidze et al. (1987a). The compo-
The substitutedgermacradiendiolwas characterizedby MS,
sition of this water water-soluble fraction was found to be: 1H-NMn and 13C-NMR.This wasthe first time this unusual
1,8-cine ole (49 .8- 66. 0% ) bor neol( 0. 1- 1. 3ol. ) oxygenatedsesquiterpenehas been found in nature.
hexanol(0.2-0.8'l") o-terpinylacetate(7.9-12.6%) A sampleof laurel leaf oil, which was produced in Israel,
bornylacetate(0.1-0.3%) nerol(0.1-2.6%) wasfound to contain a low level of o-terpineol (0.77o).Ravid
linalool(4.4-73%) methyleugenol(2.1-6.90/")
et al. (1995) found that its elantiom"ri" dirttibt,tion was
terpinen-4-ol(7.6-9.7%) eugenol(4.7-4.8%)
( + )-4R-o-terpineol (20Vo): (-) -4S-u-terpineol (807o).
Table XVll. Changes in percentagecomposition of oils produced from young (Y) and adult (A) leaves
overa full season
April July October December February
Compound Y A Y A Y A YA YA
a,-pinene 0 .3 3 .2 3 .8 2.2 3.0 3.2 4.0 2.0 3 .2
B-pinene 0.2 +.J 2 .9 3.1 4.4 5.0 4.0 6.4 4 .9
sabinene 0 .1 o.+ 7 .6 7.9 6.4 7.2 6.8 6.3 8.2 7 .5
1,8 -cin eo le 2 .7 36.9 30.2 \tI.l 40.2 39.0 40.7 A1 <
39.1 40.6
linalool 0 .3 4. 8 4 .8 4.8 5.0 5.1 3.8 5.8 5.8 4 .6
terpinen-4-ol 25.5 5. 6 4 .3 5.3 3.1 6.2 4.1 +.J 5.8 4 .2
B-caryophyllene ot.z 0. 7 1 .1 0.2 0.6 0.3 0.2 0.4 0.9 0 .5
0,-terpineol 3. 2 0. 9 0 .9 0.8 0.1 0.4 0.5 0.5 0.5 0 .7
o-terpinylacetate 1. 7 19.6u.s., 22.8 14.4 tc.J t+.J 15.3 12.1 13.3 1 3 .8
selinene* 6. 0 0. 1 0.2 0.1 0.4 0.1 0.2 0.2 0.2 0 .1
y-cadinene 10. 5 f.2 0 .1 0.1 0.3 0.1 0.1 0.1 0.2 0 .1
methyleugenol 0. 3 5. 1 b. I 5.6 8.3 7.2 8.9 8.4 6.8 7 .8
* correctisomernot identified;
Y = youngleaves;
A = adultleaves
304
\-L.oira 1995,Zygadloet al. screeneda number of essential N. A. Kekelidze, M. I. Dzanikashvili and V. V. Kutateladze,
: L tbr their antioxidant activity. In this study. the authors Composition of the water soluble fraction.sof Laurus nobilis oil.
snl,r,.redthat an oil ol Lauru,s nobilis exhibited significant M a s l o - Z h i r .P r o m . .( 4 ) , 2 4 r 1 9 8 7 i ) .
.urtioridantactivity.The major constituentsof this oil were: N. A. Kekelidze,M.I. DzanikashviliandV. V.Krtztel,adze.Dunatn-
ics of accumulation andformation ofthe essential oil compisition
camphene(1.5%) linalylacetate(5.1%) in Luuas nobilis leaoesduringontogerzesis.Fisiolgia, Bichimis.
lpinene (15.3olo) terpinen-4-ol(4.1%) Culturnich Rast.,(6), 606-614 (198fu).
'1-8-cineole(13.3%) cr-terpineol
(4.3%)
.iterpinene(1.4%) P. Kreis, U. Hener and A. Mosandi, Chirale lnhaltstffi ritherischer
eugenol(30.0%) Ole. lll Stereodffirenzierung uon a-pinen,""ftpinen und
lrnalool(12.2%)
Limonen in rithertscher Olen, Diogen uni Fe,tigarzneimitteln.
Deut. Apoth. ztg., t3o,985-988 (i990).
The following year, Ravid et al. (Igg6) examined the
A. Bernreuther and P. Schreier, Multiclimensional gas chroma-
enantiomeric distribution of borneol in Laurus nobilis oil.
I ogra ph y / rut ss sp ecf ro mef r y : A p o u.c I t ooI r t h e'di rect ch i ra I
L sing chiral GC analysis on a permethylated fu fo
B-cyclodextrin eualuation oJ-aromacompounds in plant tissues.lL Linalool in
colunrn, borneol which was found at a level of 0.2Va in the essentialoilsandfruits. Phyochem. Analysis,2, 167-170(f 991).
'ril had the following distribution: (1R)-(+)-borneol (40Vo) : G. Appendino, S. Tagliapietra, G. M. Nano and M. Cisero, A
I S - (-)-bo rne ol t60 % a) . sesquite:ene alcoholfrom the fruits of Laurus nobilis. phl,to-
c h e r n i s t r y3. 1 . 2 5 3 7 - 2 - 5 3(81 9 9 i ) .
\. -{. Kekelidze, Comparatiue inuestigation of the chemical j. A. Zygadlo,A. L. Lamarque, D. M. Maestri and N. R. Grosso,
contposition of essential oilsproduced fiom the lbaaes,stemsand
Empleo de aceitesesencialescoma antioxidantesnaturales. Grasas
indu,strial uastes of Laulus nobili,s."tr'. Gruz. Nauch-Issled. Inst.
Aceites,46, 285-288(1995).
Pishch.promProm., (3), 287-302 (1967).
\\-. G. Pruidze, S. G. Tukvadze and N. A. Kekelidze, The chanse in U. Ravid, E. Putievsky and I. Katzir, Determlnatior.t of the
enantiomeric composition of la-tetyineol in essentialol1s.Flav.
essen_tialoil composition on storage of the leates of Liurus
Fragr,J., r0,281-284 (1995).
nobilis.Tr. Gruz. Nauch-Issled.Instlpisirch. prom., (5[ 151-lb5
( 1 97 1). j. A. Zygadlo, A. L. Lamarque, D. M. Maestri and N. R. Grosso,
Empleo de aceitesesenciale,s
comoantioxidantesnaturales. Crasas
\.,\. Kekelidze,L. B. Beradzeand M. I.
Jamikashvili, Essentialoils Aceites,46, 285-288 (1995).
of Lmtrusnobilisfruits. Maslo-Zhir. Prom. (l), 32(t977).
U. Ravid. Putievsly and I. Katzir, Stereochemical onalysis of
\. A. Kekelidze, Production of Laurus nobilis leaf oil
from fresh borneol-E.
in essentiai oils usingpermethylated pcqctodexirin i
nnterial. Maslo-Zhir. Prom., (10), 28 (19S5).
a chiral stationary phase.Fliv. Fragr. J".,ff, 19l-19S (1996).
\. A. Kekelidze,Essentialoilsoftheba&, u;oocland stemof Laurus
nobilis. Khim, prir. Soedin.,(3), 457-459 (1987).
305
Progress in Essential Oils
fromPerfumer
Reprinted & Flavorist, 1999,Vol.24,No.6, P. 45
November/December
Wormseedor Chenopodium
Oil limonene(29.2%) p-mentha- 1(7),8-dien-3-ol
(10.0%)
p-cymene(0.2%) cls-p-mentha-2,8-dien-1-ol (1.0%)
It is well known that ascaridole,an asymmetric monoter- ascaridole(41.1o/o) trans-p-mentha-2,8-dien-1-ol
penoid endoperoxide that possessesanthelmintic proper- thymol(1.0%) (0.6%)
ties, can be found as a major component of American carvacrol(0.5%) p-menth-8-en-1,2-diol(1.3%)
wormseed o11,Chenopodium am.brosi,oides L. var. anthel- carvone(0"2%) p-mentha-2,8-dien-1,4-diol (0.5%)
trans-caweol(1.57") 1,4-epoxy-p-menthanediol (0.5%)
mintianm (L.) Gray lsym.Teloxysambrosioides(L.) W. A.
(9.5%)
lrans_isocarveolr
Weberl (Tucker and Maciarello, 1998).In addition, another
variety, namely C. ambrosioides var. ambrosioides, pos- name,possiblya dihydrocarveol
t incorrect isomer
sessesan oil that is low in ascaridole. A survey of the In 1984,Johnsonand Croteau examinedthe biosynthetic
literature reveals that C. ambrosioidesoils have been the pathway of ascaridole in C , ambrosioides fruJt. They found
subject of some study; however, much of the work does that o-terpinene wasoxidizedby a solubleiodide peroxidase
not speakto the varietal origin ofthe analyses. to ascaridole.
In 1935, Weiland et al. reported that American worm- Four years later, Betts used the ratio of the relative
seed had been cultivated since the mid-1800s in Carroll retention time of eachcompound againstgeraniol on a polar
County (Maryland) USA, although wild forms of this phase with a non-polar phase to show that wormseed oil
plant can be found throughout the entire United States. containedascaridole(597o)andaphenol (ca.27o).Although
Weiland et al. reported that in 1930there were 139 growers the technique is academically of interest, it is not that
producing about 7 metric tonnes of oil from approximately practical because it is used by only one or two scientists
600 acres,all in Carroll County. These oils had an approxi- around the world. Also the information generated could
mate ascaridolecontent of 777o.From a yield standpoint, be easily determined using the more universally accepted
Weiland et al. noted that approximately45.5 kg of oil could retention indices.
be obtained from approximately2.3 metric tonnes of dried Okuyama et al. (1993) determined that ascaridole
plant material in seed. Furthermore, it was found that the was the principal pharmacologically active component of
seedwas verv rich in both oil and ascaridole. wormseed. In addition to characterizing ascaridole, the
In 1974, Gupta and Behari determined that an oil pro- authors also determined that a hexane extract contained
duced from C. ambrosioldescollected from wild-growing t r ans -pino car-vylhydrope roxide, which was identified after
plants in India contained the fbllowing constituents: conversionto 1rans-oinocar.reol.
xyleneisomers(6.8%) This same year,ZLuet al. (1993) reported the analysisof
p-cymene (8.8%) an oil of C. ambrosioide,sof Guangzhou. The compounds
(83.5%)
ascaridole identified were:
acids(2.0%)
crterpinene(1.62'/") terpinen-4-ylacetate(81.62'/.)
They found that heptanoic and octanoicwere the major p-cymene(1.88%) carvacrol(0.23'/.)
acids present, although small amounts of hexanoic and an 1,8-cineole(0.32o/o) thymol(0.90%)
unidentified acid were alsopresent. It should be noted that yterpinene(0.10%) ascaridole(6.24%)
(0.33%)
cr-terpineol ledol(0.55%)
the occurrence of xylene isomers in chenopodium oil was
not unequivocally proven by Gupta and Behari. The occurrence of terpinen-4-yl acetateas a major con-
Four years later, Umemoto (1978) found that an oil stituent is very unusual.This requires corroboration before
oroduced from C. ambrosioides var. ambrosioides con- it can be acceptedas a new chemotype of wormseed.
ialned the followins constituents: A samoleofwormseed oilwas screenedfor its antimicro-
cr-pinene(30.3-33.4%) pinocarvone(20.2-65.1 %) blal activity by Bourrel et al. (1995). The oil used in this
B-pinene(0.1-0.3%) pinocarvggl. (2.4-42.6"/") screeningwas analyzedby GC/MS and found to contain:
myrcene(0.2-0.3%)
(10.0olo)
o(-p;nene limonene(6.0ol.)
*correct isomer not identified camphene(0.2%) yterpinene(0.1%)
sabinene(0.2%) linalool(0.6%)
Two years later, PascualT. et al. (1s80) determined that B-pinene(0.3%) pinocarveol.(3.9%)
an oil of C. ambrosioides var. anthelminticum of Spanish myrcene(0.7%) dihydropinocarvonet(4.0%)
origin contained: p-cymene(18.0%) p-cymen-B-ol(2.0olo)
306
a-terpineol
(1.9%) thymol(2.0%)
methylthymol(2.8%) caNacrol(4.2/") Table l. Percentagecomposition of the
ascaridole
(4.1%) oil ot Chenopodium ambrosioides and
commercial wormseed oil
-correct isomer not identified
It should be noted that the level of ascaridolefound in Compound C. ambrosioides oil Wormseed oil
this wormseed oil is considerablylower than normally en- dimethylsulphide 0.01
countered.As a result, this r,vormseedoil is believed to have tricyclene 0.22
originated from C. ambrosi,oidesvar. ambrosioitles. cx,-prnene 0.82 0- 3. 18
Also in 1995, Sagrero-Nievesand Bartley analyzed an cr-fenchene 0.02
oil produced from C. ambrosioides var. ambrosioides ol camphene 0.14
Spanishorigin. They found that the oil contained: B-pinene 0.18
sabinene 0.01
methylhexanoate(0.06%) dihydrocarveol(0.71%) 6-carene 0.03
o-thujene(0.26./.) trans-carveol(2.28%)
myrcene 0.01
o-pinene(0.09%) nerol(0.41%)
cx-phellandrene 0.01
B-pinene(0.06%) cls-carveol(4.91./")
O-terpinene
myrcene(0.03%) 17.54 12.24-1;.71
caryone(2.07%)
limonene 42.32 5.73-11.56
o-phellandrene (0.01%) geraniol(4.30o/o)
o,-terpinene (0.83%) geranial(5.00olo) B-phellandrene 0.09
p-cymene(0.03%) isopulegylacetate(0.08%) 1,8-cineole 0-6.32
limonene(32.50"/.) carvoneoxide(0.16%) Y-terprnene 0.58 0.09-1.1 6
y-terpinene (0.03%) nerylformate(0.02%) p-cymene 8.09 12-78-18.22
frans-sabinene hydrate lavandulylacetate(O.02./.)
terpinolene 0-0.37
(0.06%) isobornylacetate(0.20%)
frans-limonene oxide 0.09
cls-linaloolox;69+(Q.21%) perillylalcohol(0.15%)
benzaldehyde 0-0.39
linalool(0.07%) undecanal(0.14%)
norbornylacetatet(O.02./.) nerylacetate(0.01%)
lrans-dihydrocarvone o.on
allyllevulinatet(0.04%) geranicacid(0.04%) caryone 2.28 0.38-0.44
cls-p-mentha-2,8-dien-1 -ol methylundecanal-(0.03%) lrans-carveol 1.06
(4.00%) isobornylpropionate(0.06%) c/s-carveol 0.25
lrans-pinocarveol (26.7lok) B-caryophyllen e (2,09o/") ascaridole 1.98 16.20,4;.1o
camphor(0.84o/o) B-copaene(0.04%) eugenol 0- 0 .1 5
frans-verbenol (1.21%) cx-guaiene (0.24%)
thymol o-o2 o.17-0.23
isopulegol(3.54o/o) allo-aromadendrene (0.02.,"7
carvacrol 0.04 0.34-0.47
isoborneol (0.22%) 6-cadinene (0.08%)
menthol(1.64%)
* correct
isomer not identified
t tentativeidentification
+ luranoid form T. J- Betts, Characterization of uolatile oil constituentswith relatiuelq
Iong gaschro nnto grupl ic retention tirne,son tu;ostatirntary plmsei.
More recently, Tucker and Maciarello (1993) examined
. f. C h r o m a t o g . . 4 4 9 . 2 1 2 -l 2
6 rlgSS/.
the composition of a lab-distilled oil of the flowering tops of
E. Okuyama, K. Umevama, Y. Saito, M. Yamazaki and M. Satake,
C. ambrosioides and compared it with two commercial Ascarirlole as a pham'mcologicallyactiue principle of "paico", a
r,,,ormseed oils. A summ^ry of th"l. analyses can be seen in medicinal Pentuian plant. Chem. Pharm. gu[., af , 1309-1311
Table I. (1ee3).
L-F. Zhu, Y-H. Li, B-L. Li, B-Y. Lu and N-H. Xia,Arolraticplants and
G. S. Weiland, L. B. Broughton and J. E. Metzger, WomaseerJoil
e,ssentialcon,stituents.South China Institute of Botany, Chinese
otion. Brtlletin N o. 3B4.Univ. M arylandAgri c. Erpt. Station,
pro_chr
Academy of Sciences,Hai Feng Publish. Co. distributed by peace
CollegePark, MD, Juiy (1935).
Book Co., Ltd., Hong Kong (1993).
G. S. Gupta and M. Behari, Indian chenopodiuntoil.Indizur per{uni.,
C. Bourrel, G. Vilarem, G. Michel and A. Gaset,Etudedespnntridtd,s
r8(2),40-43(1974).
bacteriostaticlues et fr.tngistatiques en Milieu solidz rJe 24' Lruiles
K. Umemoto, Essentialoil of Chenoy:od)umornbrosioidesL. containing essentiellesprdamblementanafusdes. RivistaItal., EppOS, No. 16,
(,-)-p_irtocar"ueol
as a mrlor componcnt. Nippon Nogei Kagaku 3-12r1995r.
Kaishi,52, 149-153(f978).
L. Sagrero-Nievesand J. P. Bartley, Yolatile constituents
frc.trnthe
J. dePascualT., I. S. Bellido, C. Torres and M. A. Pdrez,Essentialoil leat:esof Chenopod)urnambrosioidesL.f . trssent.Oil Re;., 2,221-
from Chennpodium ambrosioldzs.Rivista Ital., EPPOS, 62, 123- 223 ( I egs).
f25 (1980). ra
A. O. Tucker and M. J. Maciare\lo, Someturtc atlinary herbsin Nonh
M. A. Johnson and R. Croteau, Biosqnthesisof ascaridole: lodidz America. In: Food Fknors. Fttrntation. Analysi.sancl packcLging
p e ror-itlt se-cataly :c d sy nthesis of a monotetyene er-tdop eroride Influence,s.
Edits., tr. T. Contis, C-T. Ho, C.-J. Mussinan,T. Hl
i n soluble (.\! rort s,,f CI u-n,'pttl i u m atph rcsioidesy'zlt. A rt.lriv. "1OI-4L1,
Parliarnent, F. Shahidi and A. M. Spanier, Elsevier,
Biochem.Bioplrys.. 135 254-26n,l9s+, Arnsterdam(lgg8).
307
Angelica Root and Seed Oils
Angelica root and seed oils are obtained lrom Angelica
nrchangelicaL. ssp.angelica var.satiaa (Miller) Rikli. Also
known areA. archangelica ssp.archangelicavar.noraegica
(Rupr.) Rikli and A. archangelica ssp. litoralis (Fries)
Thellung; however, their oils have not achieved any com- ! s0.0% 2t 42.0% U 4.o.
al r?e:
mercial imoortance.
In 1996,Gawdzik et al. analyzeda supercriticalfluid CO,
extract of the seeds(fruit) of A. archangelicausing GC and
GC/MS. The compounds identified were,
o(-prnene B-gurjunene
6-methyl-5-hepten-2-one trans-o-bergamotene 4t 3.504 !: 0.S% y t"u
myrcene d-numutene
5-3-carene Figure1.Thestructuresof the macrocycliclactones
Y-muurorene
o-phellandrene ar-curcumene in angelicarootoil withtheirpercentage
distribution
p-cymene in the macrolidefractionof the oil
B-selinene
B-phellandrene cx-selinene
(E)-B-ocimene cr-muurolene
6-2-carene(0.20%) germacreneD (0.64%)
cuminaldehyde B-bisabolene 6-3-carene(16.24%) o-muurolene (0.10%)
carvone y-cadinene
phellandral o-phellandrene(2.02'/") trans-piperitol (0.28'/.)
B-sesquiphellandrene myrcene(5.28%) (0.07%)
bornylacetate 6-cadinene
etemol
crterpinene(O.26%) sabinylacetate-(0.15%)
thymol (10)
4B-hydroxy-germacra-1
limonene(6.56%) carvylacetate*(0.21o/o)
carvacrol 5- Otene I
a-cubebene spathulenol B-phellandrene(1.26"/") cuparene(0.03%)
(Z)-B-ocimene (0.05%) ^y-elemene (0.06%)
0-ylangene p-elemenone.
(I-copaene (Z)-cx,-santalol 1-terpinene(3.07%) p-cymen-B-ol (0.65%)
(E)-B-ocimene (trace) m-cymen-8-ol(0.23%)
B-bourbonene methylpalmitate
p-cymene(6"39%) perillylalcohol(0.10%)
xanthotoxin
p-mentha-2,8-diene (1.57%) caryophylleneoxide (0.04o2"7
longifolene bergaptene
terpinolene(O.B7o/o) humulenol* (0.09%)
B-caryophyllene menthone(0.08%) T-atlantone(0.03%)
longicyclene (0.07%) humuleneoxide.(0.39%)
t also known as germacrene D-4-ol cx-copaene (O.57%) copaenol*(0.O4%)
l i n a l o o(l 0 . 1 4 %) tridecanolide (0.56%)
Although the authors did not present quantitative data, cls-p-menth-2-en- 1-oI o,-copaen-1 1-ol (trace)
they did shorv from the chromatogram presented that the (0.50%) methyltridecanolide(trace)
B-phellandrene, s-copaene, o(-humulene, B-bisabolene bornylacetate(1.78%) cr-copaen-B-ol (0.24o/o)
and spathulenollevelswere typical for an angelicaseedoil. B-copaene (0.16%) spathulenol (0.14o/o)
terpinen-4-ol(0.08'/") o,-muurolol (0.08%)
To demonstrate that a root oil of A. archangelica ssp.
irans-p-menth-2-en- 1-oI T-muurolol(0.03%)
archangelica var. noraegicc has a different composition (0.0e%) B-eudesmol(0.49o/")
from that normally encounteredin commerce, Bernard and verbenylacetate*(0.39%) T-cadinol(O.04%)
Clair (1997) analvzed a lab-distilled root oil of same and cr-humulene (0.54%) o-cadinol(0.06%)
found that it containecl: eucarvone(0.41%) elemol(0.05%)
o-terpineol(0.40%) cyclopentadecanolide (0.85%)
o-pinene(9.8%) (E)-B-ocimene (0.9%) borneol(0"19%) heptadecanolide (0.37%)
camphene(0.5%) cis-p-menth-2-en-1 -ol (5.1%) 8-elemene(0.42%\
myrcene(2.9%) frans-p-menth-2-en- 1-ol (4.4%)
6-3-carene(13.0%) p-mentha-2,8-dien-1 -ol (8.6%) " correct isomer not identified
t = trace (< 0.01%)
p-cymene(2.3%) cis-piperitol(2.5%)
limonene(7.3%) p-cymen-B-ol(3.9%) The same authors also compared the oil composition
B-phellandrene(2"0%) bornylacetate(4.1%) of the various underground parts ol A. archangelica, the
(Z)-B-ocimene(0.5%)
resultsof which are found in Table IL Becauseangelicaroot
This same year, Chalchat and Garry (1997) collected A. oil of commerce is usually rich in c- and B-pheilandrene,
archangelicaroots (with no subspeciesor varietal differentia- it is deduced that the oil examined by Chalchat and Garry
tion) liom the French Massif Centrd Region and subjected probably originated from A. archangelica ssp.archangelica
them to steamdistillation. The resulJantoilwas analyzedbyGC var. non)egica and not A. archangelico ssp. archangelica
and GC/MS and the constituentsidentified in it were: var. satiaa.
Schultz and Kraft (1997) obtained a commercial sample
tricyclene(0.04%) cam$hene(1"88%)
o-pinene(32.19'/.) of angelica root oil and by a combination of fractional
B-pinene(1.54%)
0-thujene(0.13%) sabinene(0.46%) distillation and silica gel column chromatography they
a{enchene (0.05o/.) (0.48%)
isobutylbenzene obtained a fraction that was rich in macrolides.GC and GC/
308
Tablell. Percentagecomposition Tablelll. Percentage
compositionof chiral
of variousundergroundparts and non-chiralmonoterpene
hydrocarbonsin
ot Angelica archangelica Finnishangelicaroot extracts
Compound Rootlet oil Root oil Tuber oil West Lapland North Lapland
Compound extract extract
o-pinene 28.08 28.65 22.21
a-thujene (+)-o-thujene I t
campnene 1. 17 1. 46 0.95 (-)-othujene 6.1 3.6
B-pinene 1. 20 1. 27 1 .06 tricyclene t i
309
f. Gawdzik, M. Mardarowicz, Z. StptTnowicz, S. Kawka and s-terpineol eudesmol*
T. Wolski, Supercritical flaicJ ertraction of essential oils from. the borneol limonenediol-
fruits on Angelica off Hoffm. and their characterization by decanol 2,6-dimethyl-2,7-octadien-1
GC/MS. J. High Resol.Chrornatogr.,19,237-240 (f996). citronellol 6-diol
C. Bemard and G. Clair, Essentiol oilsfromthree Angelica L. species trans-p-mentha- 1(7),8- eugenol
growingin Fronce. Pott 7. Root oils. ]. trssent.Oil Res.,9, 289-294 dien-2-ol thymol
(i997). geraniol carvacrol
p-cymen-B-ol mesityloxide
J. C. Chalchatand R. P. Garry, Essentialoil of Angelica roots (Angelica cls-carveol 1,8-cineole
archangelicaL.). Optimization of distillation,location in plant and nerol myrceneepoxide-
chemicalcorrytosition.l.Essent.Oil Res.,9, 311-319(1997). benzylalcohol linalooloxide*r
K. Schultz and P. Kraft, Characterization of the macrolifufruction of undecanol ocimeneepoxide.
angeliccrroot oil and enantiomeric composition of 12-methyl-13- cis-p-mentha-1(7),B-dien-2-ol methylcarvacrol
tridecanolifu.J. Essent.Oil Res.,9, 509-514(1997). limonen-10-ol isovalericacld
Y. Holm, P. Vuorela and R. Hiltunen, Enantiomeric conryosition of perillylalcohol 2-methylbutyric acid
monoteiTene hydrocarbons in n-hexane extracts of Angelica nerolidol. linalooloxide.*
archangelicaL. rootsand seeds.Flav. Fragr. J., 12, 397-400(1997). elemol ascaridole
globulol caryophylleneoxide
spathulenol 9-cyclodecanolide
YuzuOil T-cadinol caprylicacid
cr-cadinol capricacid
In 1983, Watanabe et al. analyzeda diethyl extract of the
fresh peel of Citrus junos Tanakausing GC, GC/M S and IR * correctisomernot identitied
combined with fractional distillation and silica gel column f furanoidlorm
+ pyranoid{orm
chromatography.The compoundsidentified in the oil were:
Basedon the chromatogramspresented,the major com-
ct-prnene fenchone
camphor ponents of the oil were limonene, y-terpinene and linalool.
B-pinene
sablnene dihydrocarvone* The identification of 2,6-dimethyl-2,7-octadien-1,6-diol,
myrcene cryptone which was found to be the most imoortant odorous com-
o,-phellandrene piperitone pound in ytrzu.was confirmed by slnthesis.
0,-terpinene carvone
The followingyear, Flament and Ohloff (1985) stated
limonene hexanal
heptanal that undecatriene had been identified in luzu peel oil by
B-phellandrene
ocimene* octanal Escher, although the information was not published.
y-terpinene nonanal In 1989, Sawamuraet al. compared the composition of a
p-cymene 2-octenal* supercritical CO, fluid extract of 1.Lrzupeel with a solvent
terpinolene decanal
extractand cold-pressedoil, both made from the samebatch
6-elemene 2-nonenal*
ct-copaene undecanal of {resh luzu peel. The resultsof this comparisonare shown
o-bergamotene* 2-decenal* in Table V
B-caryophyllene dodecanal The following year Tajima et al. (1990) identified the
y-elemene 2-undecenal* aldehydesin luzu oils produced from green and yellow peel
B-farnesene* 2,4-decadienal-
of C.iunos. The aldehydic compounds characterizedin the
germacreneD perillaldehyde
muurolene' tridecanal tvvooils can be seenin Table VI. Furthermore, Tajima et al.
bicycloelemene 2-pentanol determined the odor threshold of the more important alde-
cx-farnesene* amylalcohol hydes.As can be seenfrom TableVII, the odorvalue or odor
B-sesq rene
uiphelland 2-pentenol- impact of the various aldehydescan be seenas a measureof
T-caornene (E)-3-hexenol
the concentration divided by the odor threshold. F rom this
calamenene* 2,5-dimethyl-2-vinylhexanol
bicyclogermacrene (Z)-3-hexenol data,it is obviousthat B-methylnonanaland 8-methyldecanal,
hr rlrrl rnotaia (E)-2-hexenol which had not previouslybeenidentifiedin nature, were the
6+hr/l
^rhr^a+a
heptanol most odor impactful components identified in the oils.
hexyl acetate frans-sabinenehydrate In 1994, Yukawa et al. examined a peel oil of yuzu and
(Z)-3-hexenylacetate linalool
found that it containeir:
hexyl butyrate cis-sabinenehydrate
(Z)-3-hexenylbutyrate octanol ct-prnene linalool
n6r r r l r n6la+ a 2-pinanol B-pinene B-caryophyllene
geranylacetate terpinen-4-ol sabinene (E)-B{arnesene
limonen-10-yl acetate 8-dien-1-ol
76a5fr-mentha-2, myrcene o-terpineol
methylpalmitate 1-
3,/-dimethyl-5-oxo- limonene germacrene D
ethyl palmitate octen-3-ol B-phellandrene bicyclogermacrene
methyljasmonate nolanol T-terpinene germacreneB
4-methylpentan-2-one 1-ol
crs-p-mentha-2,B-dien- p-cymene globulol
6-methyl-5-hepten-2-one B-terpineol" terpinolene thymol
2-nonanone limonen-4-ol 6-elemene
310
Table V. Co.mparativepercentage
composition Table.Vl..percentage composition
of an oit and extracts of the-fresh p:;i;' ' of the
ol Citrus junos ajdehydes found in yuzu oil produced
rrom green- and yellow_colored
fruit
scF CO2 Solvent Cold-pressed
Compound extract Aldehyde Green fruit oil
extract oil Yellowfruit oil
cr-ptnene 0.64-0.90 hexanal I
0. 97 0. 95- 1 . 1 1 t
B-pinene 0.28-0.37 (E)-2-hexenal
0.36 0.32_0.35 I I
myrcene 1. 05- 1. 63 neptanal
1. 51 1. 41_.14 3 1 I
limonene 61.91-75.74 octanal 0.0068
71.04 60.41_71.29 0.0 1
15
'1,8-cineole 6-methyloctanal
3.70-5.80 6.44 6.15-8.25 0.0005 0.0006
T-terpinene 7.43-10.49 nonanal 0.0100
8.95 7.59_7.78 0.0 114
p-cymene 0. 11- 0. 48 8-methylnonanal 0.0025
o.2B 0.21-0.40 0.0021
terpinolene 0.17-0.34 citronellal
0.24 0.23_0.51 I 0.0009
octanal oecanal 0.0510
1 I t (Z)-4-decenal 0.0480
nonanal t-0.04 0.0050
I I
8-methyldecanal
0.0020
6-elemene 0.01-0.02 0. 01 0.0015
0.01-0.02 p-menth-1 0.0007
decanal t-0.03 -en-9-al
t I
I I
linalool -1.19-7.94 2.04 undecanal 0.1000
1.64-2.00 (E)-2-decenal o.0072
linalylacetate t
I I t dodecanal
0.0064
B-caryophyltene 0.02-0.19 0.09 0 .1 3 -0.17 0"0040 0.0091
terpinen-4-ol (E)-2-undecenal
0.01-0.33 0.05 t-0.02 I t
B{arnesene* 1 .4 1 -3 .4 9 cuminaldehyde I
| .cv 1.2 1 -1
.9 6 2,4-decadienal"
0.0004
o(-terpineol 0.16-0.84 0.0070
o .1 7 0.10-0.25 perillaldehyde 0.0152
dodecanal t-0.02 0.0190
t I 0.0034
piperitone t-0.07 tridecanal t
t 1 0.0002
carvone (E)-2-dodecenal
0 .0 1 0.01 0.01-0.02 I 0.0008
bicycloelemene 0.90-1.65 B-sinensal. t
0.63 0.80-1.52 I
perillaldehyde t-0.05 . correct
I 0.01-0.02 isomernot identified
ar-curcumene t I t t = trace(< 0.0005%)
trans-caweol r0.01
cls-carveol
I t
t-0.01 I t
lunipercamphor t-0.05 Table Vll. Odor value of some aldehydes
0.02 I
thymol 0 .2 4 -1 .1 0 i n yuzu oi l
0 .11 0.12-0.21
" correctisomernot identified
t = trace(< 0_0i%) Composition Odor threshold
comPound Odor
(ppm) (ppm) vatue
nonanat 100 5.000 20
Although the authors did rot present decanal 510
. any quantitative 10.000 51
data, from the chromatographic undecanal 100
d."fif* g;n it was pos_ 5.000 20
sible to estimate that, in"addition 6-methyloctanal 5
to th" j;.;" amount oi. 0.250 20
limonene and y-terpinene found, 8-methylnonanat 25
tfr" otfr". _tu;or constitu_ 0.005 5000
ents were F-pinene. myrcene,linalool, (E)_B_farnesene 8-methyldecanal 15 0.010 1500
and
Dlcycl.germacrene.Finally, the authors
deterrnined from a
CC-sniffing study that the character
impacf odo,
nent of luzu peel oil was p_menth_1-en_b_thiol. "o_po_ geranylacetate(0.14_0.17%) y-muurotene
(0.11_0.j S%)
methylN-methylanthranilare o-farnesene*
A year earlier, Huang et al. (1993) determined (0.05%)
. that over (45.36-5S.50%) nerolidol.(0.29-0.28o/")
t\\'o seasonsthe leaf oil of C,
iunos contained: B-elemene(0.19-0.39%) elemol(0.03-0.04%)
p-caryophyilene
(0.39_0.55%) B-eudesmol(0.1 o/")
s-thujene(0.25-0.63%) y-terpinene(13.62-18.46%) S-0.21
cx-plnene
(0.68-1.620/") o-humulene(0.13-0.14%)
octanol(t-0"03%)
camphene(t) terpinolene(0.42-0.52o/") - correct isomer not identilied
sabinene(0.24-0.39%) linalool(0.19-0.e1%) I = trace (< 0.01%)
B-pinene(0.86-1.56%) citronellat(0.28-0.30%) Watanabe, T. Yanai, A. Furrrhata, K_I.
myrcene(0.55-0.82%) terpinen-4-o|{0.05-0. Awano, K. Kogami and K.
06%) Hay'Nht,Volatilecomnonentsof y uzu (Cit
o-phellandrene(0.27-0.9€ /") o-terpineot ru,sjuno,1.i en,rnurting,
(0.05-0.06%)
d-rerpinene(0.09-0.i 2%) decanal(0.0710. il{ryIntemationatcn,g,i,l i;;.;i;,ii;h;, MarchI:rI7
12./.) oil rechniial "l t;;f;, p;;i ;;,
p"p'"'
p-cymene(0.71-1.09%)
linalylacetate(0.07-0.08%) A?jj)Essential st;s,,p",:
rmonene(1S.14-1B.9B%) undecanal(0.07-0.08%)
(E)-B-ocimene (9.42-5.1 Escher, cited in I. Flanent ancl
4%) nerylacetate(0.07-0.14%) G. Ohlofl Volatile cotlstituent\
of algae. Oclorifenrus constituents ,ry
rno*unitr-^it stntctun: of.
311
nor-tetpenoids identi,fied in asakusa-nori flaaour. In: Progress
Table Vlll. The principal constituents (%)
in Flarour Research 7984.Edit., I. Adda, Elsevier SciencePubl.,
in carrot seed oil and extracts produced
Amsterdam(1985).
with different solvents
M. Sawamura,T. Kuriyama, Z-F. Li and H. Kusunose,Composition of
peel oil componentsof yuzu (Citrus junos Tanaka) ertracted by
supercritical carbon dbxide andthose of traditional ones.Nippon Extracting solvents
Sholcrhin Kogro Gaikkaishi,36, 34-38 (1989). Methyl Methylene
K. Tajima, S. Tanaka,T. Yamaguchiand M. Fugta, Analysis of green Compound Oil Ethanol Freon-113 furan chloride
and yellou; rluzu peel oils (Citrus junos Tanaka). Nouel aldehgdz cr-pinene t 3.31 0.30 0.25 3.85
conTponentswith remorkably lora odor thresholds . l. Agric. Food camphene 0.70 0.25 0.18 0"19
Chem., 38, 1544-1548(1990). p-pinene 4.40 0.03 0.14 1.19
Y-2. Huang, Y-H. Cao, Q-Y. Chen and Y-L. Wq Stuclieson the sabinene 3.70 O.17 0.34 2.91 u. tc
chemical components of essential oil frorn the leaaes of Citrus
linalool 6.29 5.58 4.79 7.16 O.44
junos (Sieb) Tan ca.lanhanchergHort. Chemistry Industry Forest
geranylacetate 10.39 12.08 3.84 26.54 10.11
Prod.,13, 165-168(1993).
carotol 18.28 39.06 40.91 12.54 31.57
C. Yukawa,K. Osakiand H. Iwab:uch|Studltonthe aolatilecomponents
of quzu (Citrus junos Sieb. ex Tanaka). |apan J. Food Chem., l, t = trace(< 0.01%)
46-49 (1994).
3t2
Table X. Comparativechemical composition (%) AIso in 1995,Saadet al. collected ripe mature fruits of D.
of carrot seed oil c ssp.maximus (Desf. ) B all frorn plants grorvingwild in
lrot ?
the Akar region of northern Lebanon. Th"r"-*.r" srown rn
Wild carrot Cult. carrot an experimentalgarden and full fruiting plants, frult, stems
Compound seed oil seed oil and leaves rvere harvested and individually subjecteclto
hydrodistillation. The oils were then analyzedby CC and
o-pinene 4. 01 24.50 GC/MS and the fruit oil rvasfound to coniain:
campnene 0. 15 2.17
sabinene 0. 15 1.63 a-pinene(t) (E)-B{arnesene(0.43o/o)
myrcene 0. 13 2.95 sabinene(t) (E)-methyl
isoeugenol (37.22%)
B-pinene(t) shyobunone(0.65%)
B-terpinene" 16. 08 c. tb p-cymene(t)
y-terpinene 2.33 B-bisabolene(34.70"/.)
limonene(t) B-sesquiphellandrene (0.25%)
p-cymene o. 12 6.14 methyleugenol(1.97%) B-asarone(17.65%)
B-caryophyllene 5.29 10.26
B-caryophyllen e (1.48.k) s-bisabolene.(3.00%)
isocaryophyllene 0.35 0.45 o-bergamotene-(0.28o/o) preisocalamendiot(0.39%)
cr-humulene 0.40 0.40 0-humulene ( 0 . 3 1 %)
B-bisabolene 16.28 4.07
eudesma-4(14),11-diene, " correct isomer not identified
I J.ZJ
t = tr ac e ( < 0.1% )
linalool 0. 18 3.37
nerol For comparison purposes, the leaf and stem oils which
0.30 0.41
terpinen-4-ol 0.63 were analyzed using the same techniques were fbund to be
geranylacetateb 0.43 o.52 quite dif{'erent to the {ruit, as shown in Table IX.
neryl acetate" 19.78 More recently, Kilbarda et al. (1g96) compared the com_
24.55
carotol I. t3 c. | / position of lab-distllled fruit oils oi D. caroti L. ssD.carota
(Wild.) and D. carota ssp.satiDus (Hoffm.) Archaqg. (culti
a misidentification
basedon elutionorder
o shouldbe nerylacetate vated). The results of this study can be seen in fable X.
c shouldbe geranylacetate
As part of a cursory r"r""r-ri,-rg study on carrot seed oils
using GC and GC/MS, a number of commercial samples of
In 1995, Cil Pinilla et al, an:rlyzed three samples of this oil was found by Lawrence to possess the following
hydrodlstilled fruit oils of D. carota ssp.gummfer Hook. fil. major t,onslituenls:
that were collected in northern Spain. The oil, *"." ur-ru- cr-pinene(9.9-25.4o/o) B-caryophyllene (0.8_3.3%)
Iyzedby GC and GC/MS and found to possessthe following camphene(0.8-1.4o/o) (E)_B_farnesene (0.4_4.2%)
constituents: B-pinene(2.6-14.4%) geranytacetate(1.2_25.4%)
sabinene(6.6-20.8%) geraniot(0.5-6.2%)
uthujene (0.03-0.12%) borneol(t-0.35%) m y r c e n e ( 0 . 7 - 5 . 7 %) c a r y o p h y l l e n e o x i de ( 1 .0 _ 1 .9 % )
0-pinene(0.50-1.73%) terpinen-4-ol (0.93-8.17%) l i m o n e n e( 1. 4 - 1 7 . 1 %) c a r o t o(t 3 . 1 _ 1 5 . 0 % )
camphene(0.04-0.08%) o,-terpineol(0"16-0.69%)
6-methyl-5-hepten-2-one geraniol(0.61-2.33%)
(t-0.02%) J-Q. C", F. Perineau, M. Dehnas and A. Gaset,Extraction of t:olatile
geranial(0.14-0.32%) *ypr"":k root,^cele-ryseed.and carrot seed,by"rlifferent
sabinene(4.42-11.1So/") thymol(t-0.35%) "llooage
sol.uents.Ilr: P roct ed i ngsof I lth Intenrational Congressif Eiiential
B-pinene(0.16-1 .66%) o{erpinyl acetate(0.03-0.09%) Oil.s.Fragrancesand Flautrs, Neu:Delhi, Noa. l51g. ndits., S. C.
myrcene(0.52-0.81%) neryracetate(0.08-0.73%) Bhnttacharya,N. SenandK. L. S€thi,Vol.4, g9_97,Oxford&IBH
p-mentha-1 (7),3,8-triene geranylacetate(51.74-76.95"/") Publ. Co., Ner,vDelhi (1989).
(0.02-0.03%) cr-copaene(1-0.32%)
o-phellandrene(r-0.02%) R. K. Khanna, O. S. Sharma and A. Singh, The essentialoilfrorn the
B-caryophyllen e (0.44-1.39o/")
d-terpinene(t-0.29o/") o/") leaoesof Daucus carota Linn uar. sitiua. In, prcceedings of ltth
cr-humulene(0.24-0.61
p-cymene(0.06-2.48%) I.nlcmnti.onul Congrcs.s of EssentialOils. Fragrnn,.e.*nn'rlFiauorr,
B-ionone(t-0.50%)
lim o ne ne(0 .70 -1.1 8% ) Neu'Dclhi. Nou. 1969.Edits. S. C. Bhattuchar-i,ra, N. Sen and K.
cr-acoradiene (t-1.38%)
(Z)-B-ocimene (t) L. Sethi,Vol. 4, 173-176,O:dord & IBH publ. Co., New Delhi
B-gurjunene (t-0.16%)
(E)-B-ocimene (t-0.10%) (198e).
B-selinene(0.25-1.99%)
y-terpinene(0.02-0.52o/") cr-selinene(0.16-0.66%) M. Gil Pinilla, M. J. P6rez-AlonsoandA. Velasco_Neguer-uei a,Volatile
cls-linalooloxidet (E)-B{arnesene (0.04-0.30%) nnstihtent sfrom fruit s,'f D artcus ca r(,fo L. gumi n
(0.20-1.07%) fer H ook.fi\. J.
y-cadinene (0.07-0. 16%) E s s e n tO
. i l R e s . 7. , 4 3 3 - 4 3 5I 1 9 9 5 r .
frans-linalool oxidet nerolidol-(0.04-0.09%) H. E. A. Saad,S. H. El-Sharkawy and A. F. Halim, Essenflal oils of
(0.05-0.13%) caryophylleneoxide Dunns caroto s,sp.maximu,s.Fhar-. Acta Helv. 70, 79_S4(19g5i.
linalool(3.97-5.18%) (0.18-1.Of"/o)
c/s-sabinenehydrate V. Kilb_arda, N. Nanusevic,N. Dogovic, R.Ivanicar.rclK.Savin,Contcnt
T-muurolol(t-1.37%)
(0.o2-0.23%) ,*h::y":!yl oil of carrot aniits antibacterial actiaity .pharnane .
s-cadinol(0.10-0.90%)
lrans-sabinenehydrate 5r.777-778 1996\.
eudesm-1,1-en-4-ol (0.74-1.37o/")
(0.03-0.62%)
'correctisomernot identified
t furanoid{orm
t = t r a c e( < 0 . 0 1 % )
313
Progress in Essential Oils
& Flavorist,
fromPerfumer
Reprinted 2000,Vol.25, No.1, P. 33
January/February
TansyOil
Table l. Comparativepercentagecomposition of a
Tansyoil is obtained fromTanacetumoulgareL. (syn.Chry- Canadiantansy oil and a commercial tansy oil
santhemumaulgare(L.) Bernh.), a perennial member of the
Asteraceae family. It occurs as a weed in many parts of the Canadian Commercial
Compound oil oil
eastern United States and southern Quebec and Ontario
(Canada).The oil has been an item o[ commerce since c{,-prnene 0.5 0.2
approximately1830 (Landing, 1969).It has been produced cxthujenet o.2 0. 1
camphene z .o o.2
clmmercially in southern Michigan, northern Indiana and I
F-Pinenet T
in the eastern townships along the Quebec/Ontario border sabinene 3.9 2. 3
in Canada. 6-3-carenet I 0. 1
Although tansy exists in numerous chemotlpic forms (as or-terpinener 0.2 0. 1
will be seen in this review), the oil of commerce, which is limonene 0.1 0. 1
1,8-cineole t.c 2"3
produced in the United Statesin less than I tonne lots, is 0.3
T-terpinene 0.4
that which is rich in thujones. p-cymene 0.6 o.4
In 1961, Talwar et al. used TLC and derivatization to terpinolenet 1 I
3t4
Tabfe fl' Percentage composition of five chemotypes ot ranacetum
vulgareof Finnish origin
Chrysanthenyl Chrysanthenone
Camphor Thuione Sabinene acetate
Compound chemotype oxide
chemotype chemotype chemotype chemotype
tricyclene 0.2 0.1
cr-pinene 0.6 o.7 1.0 0.1
campnene 3.4 0.3 '1 . 1
14.0
B-pinene 0.6 0.3 0.2
sabinene 0.6
0.8 5.4 oo.c o.t
d-terpinene 0 .1 0.3 2.1
1,8-cineole 3.2 1.9
chrysanthenone oxide
3.6 i.o
48.9
Y-terpinene o .4 o.7 4.3 o.t
p-cymene 0.6 0.2 0.9 0.1
terpinolene 0.1 0.8
d{hujone o .2 0.5
Bthujone 0 .1 81.0 21.7
frans-chrysanthenol
camphor
iu
frans-chrysanthenylacetate
64.0 o.7 ri.s 0.3 11.2
prnocarvone 81.6
o.o
bornylacetate QA
trans-chrysanthenyl
frans-chrysanthenyl
propionate
isobutyrate -
i,
1.0
terpinen-4-ol 0.9 i, u.u 0.6
B-caryophyllene 0.5 o-7
thujylalcohol o.4
trans-chrysanthenylvalerate
o.u
borneol it
cadinene*
carvone
5.3 i.o 2.8
1 .3
* correct
isomernot identified
t = trace(<0.1%)
p*"
0-pinene(0.5-3.7./") trans-chrysanthenylacetate
camphene(0-0.1%) (65.6-7e.5%)
sabinene(0.4-0.8%) trans-chrysanthenylpropionate
1,8-cineole(0-3.3o/") (0.8-2.0./.)
y-terpinene(0.1-0.3%) trans-chrysanthenylisobutyrate
p-cymene(0.3-0.7o/o) (0.6-1.2o/")
B-thujone(0-0.3%) B-caryophyllene (0.3-0.8%)
frans-chrysanthenol cr-terpineol
+ lrans-chrysanthenyl
(2.4-6.5o/o) 2-methylbutyrate(0.3-0.7%) (1) e\
camphor(0.3-0.9%) y-cadinene (1.2-103%)
Figure 1. The structuresof vulgaroneA (1) and
In 7974,Fors6n and von Schantzreported their resultsof vulgaroneB (2)
the analysisof five chemotypesof T.):ulgare oil produced
from plants collected in Finland. Their rJsults are summa_ In addition to the above-listed main constituents, the
rized in Table II. authors statedthat there were at least six other chemotlpes
The followingyear,T6I6nytet al. (1975) determined the that were not identified.
main constituentsof numerousstrainso[7. oulgarecollected This sameyear, Fors6n determined that tansy could exist
from various locations in Hungarv. They can"be character_ t"r,,n*T"ro,us chemotlpic forms. He characterized the
ized as follows: rorrowlngchemotlT)es.
cr-pinene/B-pinene camphor(42.2/61 cr-prnene+ orterpineol-type aftemisiaketone-type
(14.7-23.8%) frans-chrysanthenylacetate o-pinene+ thujone-type
camphene(20.3-90.6%) (53.0%) isopinocamphone-type campnor-type
1,B-cineole(14.8-42.2%) bornylacetate(41.2%) o-pinene+ oxygenated chrysanthenylacetate-type
1-terpinene(33.3%) thujylalcohot(&.9-84.0%) sesquiterpenes-type isopinocamphone{ype
artemisia ketone(15.7-82.2o/o)borneol(23.6-54.4%) 1,8-cineole-type bornylacetatetype
yomogialcohol(18.2-2A.4%) umbellulone (22.5-81$%) chrysanthenoneepoxide-type umbellulonetype
Bthujone (29.3-94.0o/o) piperitone(23.1-64.2%) y-terpinene{ype oxygenatedsesquiterpenes-type
JIJ
Lawrence ( 1976)examineda lab-distilledoil of T.Dulsare
produced from plants collectedin Canada.The oil wasfound Table lll. Comparativepercentagecomposition of
a commercial tansy oil and a lab-distilledtansy oil
to contain: from North America
(E)-2-methyl-3-methylene- o(-copaene (0.1%)
hept-5-ene (0.1%) B-bourbonene (0.1%) Lab-distilled Commercial
cx-pinene (0.2%) camphor(6.0%) Compound oil oil
camphene(0.6%) B-copaene (0.1%)
tricyclene 0.1 0.2
B-pinene(0.1%) terpinen-4-ol (0.7%)
tx-prnene
sab ine ne(1 .5% ) 0.4 0.6
B-ylangene (0.1%)
campnene 2.5 1.8
o-phellandrene (0.1%) B-caryophyl lene (0.3olo) sabinene 6.0
limonene(0.2%) neomenthol (0.1%) 6-3-carene 0.2
1,8-cineole (0.7%) isothujylalcohol(0.4%) myrcene 0.1
y-ierpinene (0.3%) menthol(0.2%) or-phellandrene 0.9
p-cymene(0.8%) sabinol-(0.2%) 0-terprnene 0..| 0.3
terpinolene(t) germacreneD (1.5%) limonene 3.5
artemisiaketone(23.5%) carvone(6.6%) 1,8-cineole 5.1 1.8
yomogialcohol(1.1%) sabinyl2-methylbutyrate. ( 1.2%) 1-terpinene 0.5 0.4
othujone (0.9%) 6-cadinene(t) p-cymene 1.0 1.7
Bthujone (49.5%) (0.2%)
viridiflorol o(-thujone 1.2
artemisiaalcohol(1.6%) Bthujone 4.8
sabinylacetate* o.2
camphor 29.6 1.7
t = trace (<0.1%)
bornyl acetate 73.5
A year later, Uchio et al. (1977a)examinedthe composi- terpinen-4-ol 1.5
B-caryophyllene 4.5
tion of an oil of T. oulgare produced from plants grown in
umbellulone zi.z
Japan.They found that the oil contained: borneol 0.8 o.2
o-pinene(4.8%) 2-hydroxy-cr,cl,3- caryone 0.7
p-prnene(5.5%) trimethylcyclopentent-3-en- valeranone 0.4
sabinene(1.0%) 1-aceticacid-7-lactone(0.5%) thymol 6.8
1,8-cineole (9.0%) A (12%)
filifolide " correctisomernot identified
p-cymene(1.0%) o-longipinene (1.4%)
filifolone(1.0%) B-caryophyllene (0.5%) trans-chrysanthenol (1B%) artemisiaalcohol(25%)
chrysanthenone (18.9%) germacreneD (8.6%) trans-cavyl acetate (25%) ycampholenal(10%)
irans-pinocarveol (1.5%) calamenene- (1.1%) 4-thujen-2cr-yl
acetate(40%) (B%)
isopinocamphone
terpinen-4-ol (2.5%) vulgaroneA (7.60/0) davanone(95%) yomogialcohol(8%)
ketoisophorone (2.0%) v ulgar oneB ( 11. 9% ) artemisiaketone(40%)
3r6
A year later, Dembitskii et al. (1935) showedthat the oil tricyclene(1.6%) c a m p h o r( 1 7 1 %)
of T. oulgare var. boreale Fisch. differed from that of Z cr-pinene(3.0%) thujone.(7.3%)
xulgare var.oulgare. The compounds identifie dinT. tsulgare camphene(2.1%) bornylacetate(3.6%)
var. boreale Fisch., together with quantitative data for"the sabinene(1"4%) germacreneD (47.4./.)
1,8-cineole(10.2o/.) campherenol (3.0%)
major components,were as follows: p-cymene(1.7%)
o-pinene(3.0%) ar-curcumene *
camphene(9.0%) correct isomer not identified
g-calacorene
B-pinene 1,8-cineole
(14.0%) In contrast, the umbellulone-rich strain possessedthe
sabinene artemisiaketone following composition:
y-terpinene Bthujone(1.5%)
p-cymene artemisiaalcohol Iricyclene (2.2/o) camphor(3.2%)
0-yrangene camphor(53.0%) u-pinene(1.7%) thujone.(12.20/")
c[-gurJunene bornylacetate(4.0%) sabinene(8.0%) bornylacetate(2"9%)
B-gurjunene terpinen-4-ol 1,8-cineole (5.3ol.) umbellulone(56.8%)
B-caryophyllene borneol(6.0%) p-cymene(2.0%) borneol(3.6%)
allo-aromadendrene d,-terpineol
s-humulene nerol * correctisomer
not identified,
althoughpresumed
to be p_thujone.
B-bisabolene carvone
Also in 1989. Holopainen compared the composition of
.
Only quantitative data for the major components was oils produced from the leaves flo-", heaclisof three
presented.
"rid
clonesof T. aulgare using a combination of GC and GC/MS.
In 1987, Holopainen et al. discussedthe occurrence of A summary of the results of this study can be seenin Table
chemotlpes of tansyin Finland. They statedthat there were IV As can be seen, the Leaf oils weie mainly qualitatively
eight well-defined chemotlpes, e.g., similar to the Flower oils but quantitatively dlff"r"rri.
However, the three clones were found to possesswidely
sabinenetype bornylacetate-type
thujone-type
differing oil composition.
0-prnene-lype
umbellulone-type 1,8-cineole{ype Four tansy oils produced from plants harvested in
camphor-type germacreneD-type Belgium were subjected to analysis by Depooter et al.
(1989). Using a combination of GC (retention indices) and
They also noted that there were numerous mi_xedsub-
CC/MS (component identification), the four oils were
tlpes containingmore than one of thesemain constituentsin
examinedand compared.The resultsof this study are shown
major amounts.
in Table V
Ayear later, Gallino (1938)reported that a lab-distilledoil
A year later, Hendriks et al. (19g0) examined oils
oftansyproducedfrom plant maierial harvestedin the Tierra
produced from 14 collections of Z oulgare collectedfrom the
del Fuego region of Argentina was found to contain:
northeastern part (Drenthe) of the Netherlands. The oils
o-pinene(t) Bthujone(91.65%) were analyzedby GC and GC/MS. The authors compared
B-pinene(t) umbellulone (t) the composition of the Leaf oils with the Flower oiifrom
sabinene(0.97%) pinocarvone (0.15%) each of the collections and found that the Flower oils were
myrcene(trace) terpinen-4-ol(0.39%)
oterpinene (t)
richer in the main constituentthan the Leaf oils. A summarv
c[-terpineol
0
limonene(t) sabinol.(0.17o/o) of the compositionsof the various tansy oils can be seen in
1,8-cineole(0.83%) germacreneD (0.55%) TablesVI-XV As can be seen, Hendriks et al. identified 10
y-terpinene(0.25./.) myrtenol(t) chemotlpes as outlined below:
p-cymene(0.32%) eugenol(0.12./")
terpinolene(t) carvacrol(t)
1. lyratol and lyratyl acetate
o-thujone(0.760/0) 2. chrysanthenoland chrysanthenylacetate
* correct
3. B-pinene and camphor
isomer not identified
t = trace (<0. 1%) 4. artemisiaketone and chrysanthenylacetate
5. chrysanthenylepoxide and artemisiaketone
Variations in the composition of oils produced from the
6. artemisiaketone and camphor
flowering tops and leavesof T. oulgare found growing in Rio
7. lyralol. camphorand lyratyl acetate
Crande do Sul (Brazil)were asfollows (Siqueiraet at.,f SSS),
8. B-thujone and umbellulone
B-pinene (0.2-6.1./") 9. artemisiaketone, camphor and dihvdrocarvone
1 ,8- c ineole
( 1. 2- 2. 1 % ) 10. B-thujone and camphor
rx-+ B-thujone (80.6-91.8%) '*
This sameyear,Kreis et al. (19g0)used chiral GC analysis
Holopainen and Kauppinen (1g8g) analyzedthe oils of
to determine that the enantiomericdistribution of cr-pinene.
two chemotlpes of T. aulgare of '!'innish origin. One
chemotlpe was rich in germacreneD; the other wiasrich in B-pinene and limonene was as follows:
umbellulone. The authors found that the sermacrene (1S)-(-)-or-pine
ne (21o/o)
: (1R)-(+)-o-pi
n ene(7E%)
(1S)-(-)-B-pi
nene (29%): (1R)-(+)-B-pin
ene(71%)
D-rich strain contained: (4S)-(-)-limone
ne (20%): (4R)-(+)-timonene
(80%)
317
Table lV. Comparativepercentagecomposition of the Leaf and Flower oils of three clones of tansy
318
""'""',',,,',,,,,.
"',""''"irr"tiiililiii9ts"-
,,,,,,,,
Tabfe Vlf. Percentage composition of a Tanacetum Tabfe Vlff. Percentage composition ol a Tanacetum
vulgare oil of Dutch origin (chemotype 2) vulgareoilof Dutch origin (chemotype3)
1.0
i artemisiaalcohol
y-campholenic aldehyde
0. 2
4. 6
0. 2
2. 6
germacreneD
bicycloelemene
8.9
1.5
4.7
1
t
chrysanthenol*t 4. 2 1. 7 vulgaroneA t
campnor 5. 4 3. 1 vulgaroneB 3.6 12.7
i
prnocarvone 1. 4 1. 4 'correct isomernot ldentified
oorneol 6. 6 6. 1 .. onlyone formof
aftemisiaketoneis known
i 1-campholenol 2.2 5.7 t = trace (< 0.1%)
terpinen-4-ol 0.3 0.3
artemisiaketone** 1. 2 1. 9
chrysanthenyl acetate*t 18.3 .4. 30"9
bornylacetate 1. 5 0. 9
o-terpinylacetate *
0. 3 0. 2
B-caryophyllene 0. 2 0. 3
dar m aar ana f) 1. 4. r 1. 2
bicycloelemene 0.2 t
- correctisomernot identified,*" only one form of artemisiaketoneis known,
i presumedlo be trans-, t = trace(< 0.1%)
319
Tabfe Xl. Percentage composition ol a Tanacetum Tabfe Xff. Percentage composition ol a Tanacetum
vulgare oil of Dutch origin (chemotype 6) vulgareoilof Dutch origin (chemotype7)
Tabfe Xlf l. Percentage composition ol a Tanacetum Tabfe XfV. Percentage composition ol a Tanacetum
vulgare oil of Dutch origin (chemotype 8) vulgare oil of Dutch origin (chemotype 9)
320
Tabfe XV. Percentage composition ol a Tanacetum Table XVl. Percentagecomposition of tansy oil
vulgare oilof Dutch origin (chemotype 10) produced from plants harvested at different
maturity stages
Compound Leaf oil Floweroil
cr-prnene Start of Full End of
0. 3 o .2 Compound flowering flowering flowering
campnene 1. 4 1 .3
sabinene 3.9 2 .1 0,-prnene l .c r v o.72 1.3 0
B-pinene I I campnene 1.68 tt
o[-terpinene 0 .3 0 .2 0.27
B-pinene 0.13 t
p-cymene 0 .4 0.4 1,8-cineole+ terpinene* 5.45 3.68 3.79
1,8-cineole 0.4 0.4 p-cymene 0.37 0.98 1.33
Tterpinene 0.3 t artemisiaketone
sabinenehydrate. 4.56 9.91 1.1 6
0.4 0 .4
([thujone artemisiaalcohol 0.42 1.20 0 .2 9
0 .9 0-7
fenchone 0.19 0.45 0 .1 6
B-thujone 67.9 76.0
campnor 9.4 12.4 B-thujone 42.79 33.92 35.93
terpinen-4-ol 0.4 0 .5 chrysanthenylacetate* 15.97 21.64 13.84
bornylacetate 0 .9 1 .0 B-caryophyllene 0.38 0.65 1 .3 4
B-caryophyllene 0-7 t camphor+ unknownester 0-72 3.05 1 .6 8
germacreneD 6.5 0.3 borneol+ o,-terpineol 5.69 8.29 16 .16
bicycloelemene I I carvone 0.20 0.53 1 .5 1
' correctisomernot identified . correctisomer
not identified
t = trace(< 0.1%) t = trace(< 0.1%)
321
E. von Rudloff, Cas-liqui'dchromatographyof te:enes. PaftVIil M. Gallino, Essential oil from Tanacetum aulgare grouing
The oolotile oil of Tanacetum oul gar e L. . C an l Chem., 4 1, 1737- spontaneously in "Tierra ful Fuego" (Argentina). Planta Med.,
1743(rgffi). 54. 182 (1988).
E. Stahl and G. Schmidt, Chimische Rassenbei Atzneipflanzen' N. C. S. Siqueira.G. A. A. B. Silva,L. Bauer, C B. Alice and A' D.
Archiv. Pharm. 297, 385-391(1964). Pinto, Ciassificacaodo oleo essencialde Tanacehl'maulgare I clo
Rio Grande do Sul.Riv. Bras. Farm., 69(1/3),42-45 (1988).
E. Stahl and D. Scheu, Sesquiterpened.eriuatioein ritherischen Ole
des Rainsfams.Arch. Pharm., 30f , 306-308(1968). M. Holopainen andV. Kauppin en,Antimicrobial actiaitq of essential
oils of dffirent chemotypes of tansy (Tanacetum au,lgare L').
M. Sorsa,M. von Schantz,f. Lokki and K. Fors6n,Variability of
Acta Pharm.Fenn. 98, 213-219(1989).
essentialoil componentsin Chry sonthemumtrulgareL in Finland,
Anal. Acad.Sci.Fenn., SeriesA., 135, f-13 (1968). M. Holopainen,Comparisonbetueenflower headandleaf essential
oilof tanry (TanacetumoulgareL.). ActaPharm.Fenn.,98, 101-
W. Czuba and H. Poradowska, Comparison of the essential oil
107(1989).
composition lrom different species of Tanacehtm. Czas. Tech
(Krakow),(5), 33-35(1969). H. L. DePooter,J. Vermeeschand N. M. Schan'rp, The essentioloils
<tfTanacetumaulgare L. and Tanacetum p arthenium (L. ) Schultz-
K. Fors6n and M. von Schantz.Naue Hau'ptbestandteilein iitherischen
Bip. J. Essent.Oil Res.,1,9-13 (f989).
Ole des Rainfams in Finland. Arch. Pharm., 3O4, 944-552
(1e71) H. Hendriks, D. T.D. van der trlst, F. M. S.van Putten and R. Bos,
The essential oil of Dutch tansy (Tanacetum aulgare L.). J.
T. Lokki, M. Sorsa,K. Fors6n and M. von Schantz, Geneticsof Essent.Oil Res.,2, 155-162(f990).
monoter-penesin Chry santhemum aulgara' Hereditas, 74, 225-
232 (1973). P. Kreis, U. Hener and A. MosandI, Chiral comport'ndsof essential
oik. Patt 3. Stereodifferentiationof a- and ftpinenes andlimanene
K. Fors6n, Begleitstoffe in oerschiedenen Chemotgpe-n Don
in essential oils, piharmacognostic products and drugs' Deri'
Chry santhenw,* aulgoru II. Reine trans Chry sonthenylacetat-
Apoth. Ztg., r30, 985-988 (1990).
type. Farm. Aikak., 83, 9-17 (L974)
A. Neszm6lyi, G. W. A. Milne, B. Pod6nyr, I. Koczka and E.
K. Fors6n and M. von Schantz,Chemotypenoon Chrysanthemum
H6theIi: Composition of the essential oil of clone 109 of Tanacetum
rrulgare (t.) Bemh. In: Chemistry in botanical classification-
anlgari cLnd2D N M R inoe stigation oftmns -chry santhenyl acetate.
ndits., C. Bendz and J. Santesson,p.145-152, Academic Press, (1992).
London (1974). J. Essent.Oil Res.,4,243-250
U. Ravid, E. Putievsly, I. Katzir and R. Ikan, Chiral CC analysis oJ'
P. T6t6n1a,P. Kaposi and E .Hlthely,Variations inthe essentialoils
enontiomerically Tturefenchonein essentialoils. Flav. Fragr. J., 7,
of Tanacetum uulgare. Ph1'tochemistry,f 4, 1539-1544 ( i975 ). (1992).
r6e-172
K. Fors6n, Uber dte Infraspezifische Chemische oariation bei
U. Ravid, tr. PutievslT and I. Katzir, Determination of the
Chrysanthemumaulgare.Anal. Acad Sci. Fenn., SeriesA, 207'
enantiomeric co-poiition of (1R)-(+) and (15)-(-)-camphor in
7-51(rs75). essential olls of some Laml'aceaeand Compositae herbs. Flav'
B. M. Lawrence, unpublished data (1976). Fragr. J., 8,225-228 (1993).
Y. Uchio, M. Nakayama,A.MatsuoandS.Hayashi,Neuconstituents A. Kurowska, D. Kalemba, T. Majda, j. Gora and Z. Mielniczuk,
of essential oil of Chrytonthemum aulgare (L.) Bernh lr': Analysis of essential oils in aspectsof their influence to insects
iroceedings of Y Ii lnteriattonal Essential'1il Congress.pp' 477' Panitt. issential oil of tunsq'(TanaietumuuigareL ). Technol'
479, Kyoto (1977a). Chem.. Spozpvczka. 46. I 5-22 (1993).
Y. Uchio, A. Matsuo, S. Eguchi, M. Nakayama and S Hayashi, F. Perineau,C. Bourrel and A. Gaset,Characterisationdel'a'ctiaite
Yulgarone B, a not:elsesqiiterp eneketonefrom Chry santhemum
fongistatique et bacteriostatique de quatre lruiles essentielles
auliare and its photochetnical transformtttion to aulgarone A' riches enlactones (Aunde, Cataire, Eupatoire, Tanaisie). Riista
Tetiahedron Lett. (13), 1191-1194(1977b). Ital. EPPOS, (Numero Speciale),695-703( 1993).
G. M. Nano, C. Bicchi, C. Frattini and M. Galhno,Wildpiedmontese Essenti'aloil
J. Collin, H. Deslauriers,N. PageauandM.Gagnon,
G. 'of
plants. II. A rare chemotype of Tanacetum xulgarc L. abundant tansy (Tanacetum aulgare L.) of Canadian origin' J. Essent'
in Piedmont (Italq).PIaLta Med., 35, 270-274 (1979). Oil Res.,5,629-638(1993).
tr. H6thelyi, P. T6t6n)4,J.T.Kettenes-vanden Bosch,C. A. Salemink, R. M. Smith and M. D. Burford, GLC of supercriticalJluid extracts,
W. HeLima, C. Versiuis,I. Kloostermanand G. Sipma,Essenfial of essential oilsfrom the medicinal herb's,feoerfeu, tys gnd
oilsof fiue Tanacetun anlgare chematyT:es.Phltochemistry, 20, Cerrron chamomile.J. Chromatog. Sci.,32, 265-269 (1994).
1847-1850(1981).
C. Bourrel, G. Vilarem, G. Michel and A. Gaset,Et ude des propridtds
G. Appendino, M. G. Valle and G. M. Nano, On aneu chematype bacteriostatiques et fongistatiques en milieu solide de 24 huiles
oj i anaceatmaulgare. Fitoterapia, 53, I f 5- I 18 ( 1982). essentiellesprdamblement analysdes.Rivista Ital. EPPOS, No.
W. R. Schearer,Componentsof oil of tansy (Tanacetu-muulgare) 16. 3-12 (1995).
that repel Colorado potato beetles(Leptinotarsa declemlineata). U. Ravid, E. Putievslg' and I. Katzir, Determination-of the
(1984).
J. Nat. Prod. 47,964-969 enantiomeric compoiition of a-te:ineol in essentialoils. Flav'
A. D. Dembitskii, G. I. Krotova, R. A. Yurina and R. Suleeva,Com- Fragr.,j., 10, 281-284(1995).
position of Tanacetum oulgare esset$ialoil' Khim. Prir. Soedin , U. Ravid, E. Putievsky and I. Katzir, Stereochemical analysis of
(6), 716-720(1e84). borneol in essential oils usingper-mthylated ftcgclodextrin as a
A. D. Dembitshi, G. I. Krotova and-R. Suleeva,Composition of the chiral stati,onaryphase.Flav. Fragr. J., 11, f91-f95 (1996)
essential ttil Tanacetum aulgare aar' boreale Fisch ln Lkad'
Nauk. Kaz. SSR,Ser.Khh., (3L 75-77(1985).
M. Holopainen, R. Hiltunen and M. von Schantz,A sfady ontansy
Planta Med., 53, 284-287 (1987).
chemotype,s.
322
CajuputOil y-eudesmol(0.6%) (0.7%)
B-eudesmol
According to Brophy and Lassak(1988),until the taxonomic 0-muurolol(t) bulnesol(t)
cr-cadinol(t)
revisionof th e Melaleucagenus,there was someconfusionas
* correct
isomer not identified
to the true source ofcajuput oil. In the early literature, the r tentative identification
botanical origin of the oil was thought to be M.leucad.endron t = trace (<0.1%)
L. (Sood, 1966; Tho et aI..1985)rho*",r"r, it is now known In 1995, Ravid et al. determined that the enantiomeric
that the true origin of cajuput oil is M. cajuputi powell (s1n. distribution of u-terpineol (I0.3Eo)in a commercial sample
M. minor Smith). of cajuput oil was found to be (aR)-(+)-o-terpineol (57%) :
In 1966, Sood determined that the major constituent of (4S)-r-)-u-terpi neol A3To\.
cajuput oil was 1,S-cineole.Twenty-two yeirs later, Todorova The following year, Ravid et al. (1996) examined the
and Ognyanov (1988) analyzeda sample of Vietnamese enantiomeric distribution of borneol occurring at 2.0%oin a
cajuput oil. They found that it contained: commercial sample of cajuput oil. Chiral GC analysison a
s-pinene(3.8%) aromadendrene(t) permethylated B-cyclodextrincolumn revealedthai borneol
B{hujener(1.0%) o-bisabolene.(t) had the following distribution: (1R)-(+)-borneol (33%) :
B-pinene(2.6./") o-humulene(1.3%) ( 1S)-(-)-borneol (677o).
limonene(4.8%) allo-aromadendrene (1.5%) Also in 1996, Brophy and Doran showed that the main
1,8-cineole(48.0o/o) 6_maaliener (1.4%)
p-cymene(13.2o/o)
subspeciesfor cajuput oil production is M. cajuputi powell
a{erpineol (9.8%)
oterpinene (t) 6-cadinener(0.4%)
ssp.cajuTtutiand the distribution of this subspeciesis limited
q-p-dimethylstyrene (0.2k) geraniol(0.3%) to the Malaku (Moluccas) islands of AmLon, Buru and
5-elemene(t) p-cymen-8-ol(0.4%) Ceram. Approximately 257oof the commercial production
linalool(3.4%) B-maaliolr(0.5%) (360 tonnes) ofcajuput oil oflndonesian origin lakes place
B-caryophyllen e (2.1o/o) guaiol(0.2%)
on these three islands,although most of the oil production
B-elemene (t) bulnesol(0.2%)
terpinen-4-ol(1.6%) eudesmol.(0.9%)
comes from Buru. The remaining 75Vo is produced on
plantations in Javafrom seed coleJted fro- ihe Moluccas
- correct isomer not identified
t tentalive identification (probably incorrect) islands. A quantity (ca. 100 tonnes) is produced in the
t = trace (< 0.1%)
Mekong delta of Vietnam. Brophy and Doran comparedthe
Also in 1988, Williams et al. examined the chemical major constituentsof cajuput oils that had been graded 1-3
composition of cajuput oil and found that it contained: by Indonesiancajuput oil merchant.As can be seenfrom the
data shown in Table XVII, the oils are graded according to
cr-pinene(38.9%) y-terpinene(1.0%)
their 1,S-cineolecontent.
B-pinene(1.5%) p-cymene(3.1%)
myrcene(0.5%) terpinolene (0.8%) Brophy and Doran also analyzed a lab-dttilled otl of M.
o-terpinene(0.2%) linalool(0.3%) cajuputi ssp.cajuTtutiby GC and GC/MS. The compounds
limonene(2.9%) terpinen-4-ol(1.9%) identifiedwere:
1,8-cineole(21"1"/.) c{erpineol (3.3%)
o,-pinene (1.0%)
Two years later, Motl et al. (19g0) used a combination of a-thujene(0.2%) aromadendrene (0.9%)
CC and GC/MS to analyze a sample of cajuput oil of o-humulene(0.4%)
B-pinene(1.1%)
Vietnameseorigin. It was found to contain: sabinene(0.1%) B-farnesene.(0.1%)
o-phellandrene (0.5%) viridiflorene(6.1%)
c,-pinene(3.2%) B-caryophyllen e (2.5%) oterpinene(0.1%) oterpineol(5.5%)
camphene(t) terpinen-4-ol (1.5%) limonene(4.1%) B-selinene (0.9%)
B-pinene(0.8%) y-elemene(t) 1,8-cineole (48.8%) o-selinene(0.8%)
sabinene(t) thujopsene(t) yterpinene (0.2%) bicyclogermacrene (0.6%)
6-3-carene(t) y-curcumene(0.5%) p-cymene(0.6%) palustrol(0.1%)
myrcene(0.1%) cr-humulene (1.6%) terpinolene (0.1%) caryophyllene oxide(1.1%)
o-phellandrene (0.5%) B-guaiene- (0.3%) (I-gurjunene (0.1%) globulol(2.1%)
o-terpinene(0.6%) o,-terpineol(8.7%) linalool(0.1%) viridiflorol
(1.3%)
limonene(4.1%) cr{arnesene*(0.3olo) e (11%) spathulenol (8.3%)
B-caryophyllen
1,8-cineole (41.1./.) B-selinene (1.5%)
* correct
B-phellandrene (0.2%) o,-selinene (1.5%) isomer not identified
(Z)-B-ocimene (t) ycadinene (t) V. K. Sood, The aolatile leaf oil of Melaleuca la.rcadendron L..
yterpinene (4.6%) 6-cadinene(t) Perlum. Essenr.Oil. Rec..b7. 3b2j63 ( 1966).
(E)-B-ocimene (t) B-sesquiphellandrene (t)
p-cymene(6.8%) cadina-1,4-didhe (0"4"k) ]. j. Brophyand E. V T,assak, MelaleucalzucodendronL.leaf oil: Tun
terpinolene (5.9%) phenylprop anoid chematypes.Flav. Fragr. g, 43-46 (199g).
calamenerle.(t) i.,
p-cymenene(0.2%) geraniol(0.4%) P. T. T. Tho, L T. Thuy, N. T. Dung and e. M. L oan,pharmacological
6-elemene(t) o-maaliene.(t) action of the uolatile oil of cajuput. Rev. pharm. (Hanot), 7"6-85
o,-ylangene (0"3%) caryophyll6neoxide (0.3%) (1e85).
CI-copaene (t) elemol(t) M. Todorova and I. Ognyanov, Composition ofVietnamese essential
linalool(3.6%) guaiol( 1. 2% ) oil f ro m M eIal eucil i ucadendron L.. perfum. Flavor.. lS( I ). f7 -
B-elemene (0.3%) T-cadinotr(t) 18 (1988).
323
L. R. Williams, V. N. Home andX-L. Zhang,The
TableXVll.Gomparative percentage composition compositionand bactcricidal actiaity of oil of
of Indonesiancajuputoils M elaleucaaltemifulia (tea trea oil). Intemat. J.
Aromatherap.,f(3), 15-17 (1988).
Grade 1 Grade 2 Grade 3 O. Motl, j. HodacovaandK.Ubib Comltositionof
Vi.etnamesecajuput essentialoil. Flav. Fragr.
Compound Buru NWBuru Buru NE Buru Java Buru
J., 5,39-42 (1990).
o,-pinene 2.1 2.1 2. 5 19.5 3.8 J. l
U. Ravid.E. Putievslq'andI. Katzir,Determination
o(-thujene 0.3 0.3 0.9 0.8 1.2 ofthe enantiomeric comltosition of a-terpineol
B-pin en e 1. 1 1. 4 0.9 8.6 2.5 1.1 in essenti.aloils. FIav. Fragr. J., lO, 2BI-284
limonene 5.6 5.2 4. 9 17.4 6.9 4.8 (1ee5).
1,8-cineole 62.8 66.5 41. 6 21.5 50.7 34.0 U. Ravid, tr. Putievsky and I. Katzir, Stereo-
y-terpinene 1.2 0.9 7.4 8.7 3.1 5.0 chemical analusis oi bomeol in essential oils
usingpermefhylatedftcyclodexlrin asa chiral
p-cymene 1.3 0.5 3.5 3.0 1.4
stationary phase.Flav. Fragr. j., ll, 191-195
terpinolene 0.6 0.3 1. 0 4.1 0.5 (1996).
B-caryophyllene 3.7 3.3 6.9 2.8 4.9 7.4 j. J. Brophy and j. C. Doran, Essential oils of
aromadendrene 0.9 0.7 t- + 1" 2 0.9 1.7 tropical Asteromgrtus, Callistemon and
o,-humulene 1.8 1.9 3.9 0.1 2.3 0.3 Melaleuca species. ACIAR monograph,
viridiflorene 4.5 3.8 3 .1 1.7 2.5 Australian Centre for International Agriculfu re,
Canberra,Australia( 1996).
o{-terpineol 4.5 3.8 3 .0 1.9 3.8 2.4
324
St. John's Breador CarobExtract 2-nonen-4-yne(0.40o/") 2-(2't urylmethyl)furan (0.02%)
Thepods of St. John'sbread,carob orlocustbean (CercLtonia 3-hepten-2-one (1.00%) 2-nonanone (8.40"/")
butyl isobutyrate(t) 6-methyl-3,5-heptadien-2-one
siliclua L.) are the source of extracts used in the flavclr
2-methylpropylbutyrate (0.40%)
industry while the seedsare a source of locust bean gum. (0.03%) l i n a l o o(l1 . 0 0 %)
Little was knou'n about the volatiles of the seed-freeclarob 2-butylfuran(0.02y") 2-nonanol(1.20./")
pod until 1992when Macleod and Forcen used GC/MS to 5-methyl-2{uraldehyde (0.80%) nonanal(3.30%)
eramine the volatiles o{'rar.v carob powder. Initially they benzaldehyde (1.00%) 2-methoxyphenol (guaiacol)
heptanol(0.20%) (3.30%)
isolated the volatiles of a seed-{reecarob powcler uslng a
rsopropylbenzene (cumene) 2-phenylethanol (0.20%)
Likens Nickerson simultaneousdistillation and extractLn (0.0e%) f urfuryl isobutyrate(0.30%)
svstemwith 2-methylbutane as the solvent.A{ter removrng dimethyltrisulphide (0.20",) 2-nonen-4-one (1.20%)
"
the solvent, thev fractionated the volatile concentrate inti 1-octen-3-ol (1.00%) 3,5,5-trimethylcyclohex-2-enone
an acid fraction and a neutral fraction. The comnounds 6-methyl-5-hepten-2-one (isophorone) (0A0%)
(0.30%) methyl(methylthio)methyl
identified in the neutral fraction were as follows,
2-octanone(0.S0%) disulphide(0.04o/")
acetaldehyde(t) 4-hexen-3-one (0.01%) 2-pentylfuran (0.40"/") 3-nonen-2-one(1.70./.)
methanol(t) toluene(0.05%) octenone*(0.40o/") hexyl isobutyrale(1.40%)
methanethiol (0.O47o) 3-methyl-2-butenol (t) ethyl hexanoate (0.02%) (E)-2-nonenal (0.10%)
ethanol(t) methyl2-methylbutyrate (0.90%) butylbutyrate(t) hexylbutyrate(2.30%)
2-methyl-2-propanol (t) 2-isopropylfuran(0.01%) C. alkylbenzene"(0.0So/.) nonanol(1.20%)
'1,3-pentadiene- (0.02%) 2-octanol(0.20%) ethyl benzoate(t)
2,4,6-trimethyl-1,3,5trioxane
dichloromethane (t) (paraldehyde)(0.30%) octanal(1.00%) methyl1-(methylthio) ethyl
2-methylpropa nat (1.20%) 2-methyl-2-butenol (t) 2-ethyl-3-methylpyrazine (t) d i s u l p h i d (e0 . 1 0 %)
2,3-butanedione (diacetyt) 2-hexanone(0.10%) 2-propanoylf uran (0.20%) terpinen-4-ol (0.09%)
(0.20%) 2-propylfuran(t) isoamylisobutyrate (1.00%) 4-methylacetophenone (t)
1,1-dimethoxyethane 2-hexanol(0.10%) amyl isobutyrale(0.a0%) 2-decanone (0.10%)
(0.20o/o) isopropylisobutyrate(t) 1,4-cineole (0.30%) 2-methyl-3-(3-f uryl)propenal
butanal(t) hexanal(2.4O%) 4-mercapto-4-methyl-2- (0.08%)
hexane(0.50%) oclane (2.40"h) pentanone(0.04o/") u-terpineol(0.02%)
2-methylfuran (0"10%) ethyl butyrate(0.20%) p-cymene(0.40o/") methylsalicylate(0.01%)
2-methyl-3-butan-2-ot (0.09%) 2-methyltetrahyd rofuran-3-one limonene(0.08%) myrtenal(2.80o/")
ethylacetate(t) (0.20%) benzylalcohol(O.20%) verbenone(3.80%)
3-methylfuran(0.O2%) 2-methyl-2-pentenal (0.09%) 3-octen-2-one(0.20%) 3-phenylfuran (0.03%)
chloroform (0.10%) hexenal*(0.01%) 2,2,6trimethylcyclohexanone hydroxy-p-menth-4-en-3-one-
isobutylalcohol(0.06%) 1,3-octadiene. (0.08%) ( 0 . 1 0 %) (1.40./")
2-methyl-2-butanot (0.10%) furfurylmethylether(0.10%) 2-(2'turyl)furan (0.03%) cuminaldehyde (O.04%)
hexadiene*(0.02./.) 2{uraldehyde(furfurat)(0.90%) phenylacetaldehyde (1.30./.) phenylbutanone" (0.19%)
3-methylbutana| (4.20%) 2-isopropyl-4-methyl-1, isoamylbutyrate(0.04o/") s-octenylacetate(1.00%)
2-methylbutanal (2.40%) 3-dioxolane (0.01%) N-ethylpyrrole-2- 2-undecanone(2.60%)
1-penten-3-oi (0.30%) 1-(methylthio)butane (methytbutyl carboxaldehyd e (0.20"k) heptylisobutyrate(0.08%)
methylisobutyrate(0.S0%) sulphide)(t) amyl butyrate(0.20%) heptylbutyrateQ.20%)
2-pentanone (0.30%) alkenylfuran. (0.10%) y-terpinene(0.20%) 4-methyl-2-phenylpent-2-enal
2,3-pentanedio ne (0.02o/") (E)-2-hexenal (0.30%) octanol(1.30%) (0.o4o/")
2-pentanol(0.20./") 5-methyl-2-hexanone (t) 4-nonanone (t) octyl isobutyrate(0.80%)
pentanal(0.20%) (Z)-3-hexenol (0.09%) acetophenone (3.00%) 5-methyl-2-phenylhex-2-enal
heptane(0.40%) 1,1-diethoxybutane (t) linalooloxide.(0.30%) ( 0 . 1 0 %)
2-ethylfuran (0.10%) hexanol(1.00%) (Z)-3-hexenyl 2-tridecanone (4.0O%)
2,5-dimethylfuran (t) p-xylene(t) methoxyformate (0.20%)
3-hydroxybutanone 4-heptanone (0"01%) -correct isomer not identified
(acetoin)(0.10%) alkenylfuran- (t) t = tr ac e ( < 0.01% )
bromodichloromethane (0.10%) m-xylene(0.05%)
3-ethylfuran (t) heptanal(0.03%)
In addition, the following acids r,verefbund in the acid
methylbutyrate(0.05%) 1-hepten-3-ol (0.80%) lraction of the volatile concentrate:
heptadiene- (0.06%) 2-heptanone(4.80%) aceticacid (t) 2-methylbutyricacid (8%)
2,4,5-trimethyl-1,3-dioxolane butyl propionate(t) propionicacid (t) hexanoicacid(19.0%)
(0.20%) vinylbenzene(styrene)(0.207") isobutyricacid (45.0%) octanoicacid (0.5%)
2-vinylfuran(0.04%) 2-heptanol(2.400/") butyricacid (5.0%)
isoamylalcohol(0.50%) 3-(methylthio)propanal
4-methyl-2-pentanone t = trace (< 0. 1%)
(methional) @.05%)
(0.05%) 2-methylcyclopent-2-enone The volatiiesof raw carob powder were obtaineclby high
1,1-dimethoxy-2- (0.o2%) vacuurn distillation and subjected to analvsishv GC/MS
methylpropane(0.02%) 2-acetylfuran (0.20o/")
2-methyl-2-butenal (0.10%)
(Cantalejo, 1997). A second sample of the same lot u,as
2-methylpropylisobutyrate
dimethyldisulphide(3.10%) (0.50%) roasted at 120oC for 10-60 nin and GC/MS analysesrvere
ethyl isobutyrate(0.50%) methylhexanoate(0.80%) run. on samples taken every 10 min. A summary of the
amylalcohol(0.10%) 1, 3- nonadiene* ( 1. 30% ) analltical data obtained from raw carob pouder cornptrrecl
325
Table XVlll. Percentagecomposition of the volatiles in raw and roasted carob powder
326
Tabfe XVlfl. Percentage composition of the volatiles in raw and roasted carob powder (continued)
Table XlX. Volatiles in raw carob and its roasted powders (in ppm)
Light Medium Dark Light Medium Dark
Compound Raw roast roast roast Compound Raw roast roast roast
aceticacid 12. 7 - J. l 12.9 2tridecanone 2.2 o.7 0.9 0.7
isobutyricacid 290.6 8. 3 19. 3 2-pentadecanone 7.7 4.1 4.9 3. 3
butyricacid 14.4 2. 8 3. 1
I'
+.1 2-heptadecanone 2.4 2.1 1. 3
2-methylbutyric acid 12. 5 5. 3 4. 7 4.0 isovaleraldehyde - 0.1 0. 6
isovalericacid 3. 1 2-methylbutanal 0. 1
hexanoicacid a^ trl trA
butanol - 0.9
valericacid 7.0 2-nonanol 1.7
octanoicacid - 1 .0 1 .6 l-o 2-undecanol 0.8
methylisobutyrate I o.u 2-tridecanol 1.2
methyl butyrate 5.2 2-pentadecanol 1.4 1.6
ethylisobutyrate 0.5 allylmethylsulfide 0.6
methyl2-methylbutyrate 0.6 dimethyldisulfide 0.5
methylvalerate 0 .2 dimethylthiophene 14.8 0.7
methylhexanoate 30.7 cyclohexylisothiocyanate - t.J z .+ t.z
isopentylisobutyrate LV 2-acetylpyrrole - 1.2 2.3 1. 8
methyloctanoate 0.9 Denzene 0.1 2.3 0-4 0.2
ethyl 3-octenoate" t.J benzaldehyde 0.9 t
ociyl butyrate 0.9 benzoicacid 0.3 1. 1
fudural t-I 0.8 cuminaldehyde 2.9 1. 7
furfurylalcohol o.z (E)-cinnamaldehyde :: 1.1
5-methylfudural 2,6-ditert-butyl-p-benzoquinonei
- 0.9 t
cyclotene BHTl - t.z 1.5 1. 0
3-methyl-2,5{u randione z.u a.u 2,4-ditert-butylphenolt - 0.9
2,3-dihydro-3,5-dihydroxy-6- 6,6-dimethylcyclooct-4-
methyl-4H-pyran-4-one - t 15. 3 17.5 en-'l-one 1.2
5-hydroxymethyl-2-furfural 2.3 2,5-di-tert-amylquinonet 1.6 3.1 1.0 1. 0
limonene 5. 4 1. 2 ethylisopropylether 2.1
terpinen-4-ol 0. 9 0.5 oecane 1.0 0.4 0.9 0.5
(E)-anethole 1. 1 0.7 5-undecen-3-yne* - 0.9 0.6
carvone 1. 8 0.8 3-methyl-5-propylnonane - 0.4 0.4
isothymol - 0.6 0.9 0.8 hexadecane o.u 0.5 0.6 0.5
thymol - 0. 9 1. 1 0,7 12-methylpentadecane 0.9 0.7 0.8 0.6
eugenol 3. 1 2.0 hexahydrofarnesyl acetone 1.8 2.0 2.1 1. 5
B-caryophyllene - -t* 5' 5 2.7 octadecane 15.0 15.6 14.8 9. 2
cr-humulene 1. 5 t.J methyl14-
. 1. 3
ar-curcumene - -
1.0 methylpentadecanoate* 2.1 2.1 1.4 LZ
diacetyl 1. 0 ethylpalmitate 0.6 1.4 0.6 0.4
2-heptanone 39. 1 0 .6 0.7 methyloctadec-1 0-enoate* 1.5 2.0 0.8 0.7
2-nonanone 2.0 0 .4 0.5 o.4 * correct isomer not identified
2-undecanone t artifact
7-decen-2-one '1.1
t = trace (< 0.1%)
327
with some roasted carob powder samplestaken at 10, 30 and G. Macleod and M. Forcen, Analysis ofoolati'lecomponentsderiaed
60 min intervals can be seen in Table XVIII. frorn the carob bean Ceratonia si'li,qua.Phytochemistry, 31,
3113-3119(1992).
This sameyear,Arrighi et al. ( 1997) compared the volatiles
M. j. Cantalejo, Effects of roasti.ng tenlperahtre on the arom'a'
of raw carob powder with those of roasted carob powder iomponenti of carob (Ceratoni,a si,LiquaL.). ]. Agric. Food
of different roasting times. The volatiles examined were Chem., 45, 1345-1350(1997).
obtained by use of a purge and trap headspace system set W. Arrighi, T. G. Hartman and C-T. Ho, Carob bean aromn
at B0oC for 30 min with a nitrogen flow rate of 40ml-'/min. d,epenilpnceon roasting conditions. Perfum. Flavor., 22(1), 3I'
The results of this headspacestudy are shown in Table XIX. 45 (1997).
A comparison between this and the other data reveals a
number ofdifferences. These differences can be considered
asbeing a result of the different methods ofvolatile isolation
from the various forms of carob powder.
Progress in Ess ential Oils
Reprinted
fromPerlumer
& Flavorist, 2000,Vol.25, No.2, p.46
March/April
(1R)-(+)-B-pinene
(3%) : (1S)-(-)-B-pine
ne (97%) Zhu et al. (1995) used GC/MS to analyze a peel oll .l
(4R)-(+)-limonene
(99%): (4S)-(-)-limonene (1%) of bitter orange. The constituents identified were as
Also in 1990, Huang et al. analyzed a sample of Chinese follows:
bitter orange oil and found that it contained: c - p i n e n e( 0 . 11 %) linalool(20.69%)
camphene(0.10%) camphor(4.14o/o)
crthujene(0.22%) cis-linaloolo";6st (0.08%) B-pinene(0.50%) isononylacetatet(11.73o/o)
cx-pinene(1.17%) terpinolene (0.21"/") 6-methyl-5-hepten-2-one terpinen-4-ol (0.10%)
sabinene(0.0770) linalool(1.917a* ( 0 . 1 0 %) p-cymen-9-o1.. (0.28%)
B-pinene(0.63%) B-terpineol- (0.02%) myrcene(0.20'/") cr-terpineol(3.75%)
myrcene(1.83%) (0.01%)
citronellal p-cymene(1.01%) dodecane(0.36%)
p-cymene(0.52%) naphthalene(t) 1,8-cineole (2.48%) nonylacetate(0.620/0)
limonene(86.36%) terpinen'4-ol (0.20"/") 3,5,5-trimethylhexanolt (0.47%)
citronellol
(E)-B-ocimene (0.24%) o-terpineol(0.24o/o) ( 1 . 3 6 %) linalylacetate(30.72%)
yterpinene(4.25%) decanal(0.10%) cis-linaloolox;6st (0.81%) nopolt(0.36%)
frans-linalooloxider(0.16%)carveol*(0.05%) trans-linalool ox16st(1.02%) geranylformate(0.42'/.)
329
Progress in Essential Oils
fromperfumer
Reprinted & Flavorist,
March/April
2000,Vol.25,No.2, p.46
329
heptanal(0.08%) nonanal(0.07%)
Table l- Percentagecomposition of bitter orange o,-thujene(t) p-mentha-1 ,3,8triene(0.11%)
peel oil produced from fruit of different maturity c-pinene(0.75./.) cls-sabinenehydrate(0.66%)
camphene(0.23./.) cls-limoneneoxide (0.49%)
benzaldehyde (0.08%) frans-limonene oxide (0.28%)
Compound Unripefruit Ripefruit sabinene(0.05%) pinocarvone(0.04'/.)
c-prnene 0.36-0.40 0.37-0.39 B-pinene(2.53%) lrans-Bterpineol(0.16%)
campnene t t myrcene(1.59%) terpinen-4-ol (0.15%)
B-pinene 0"15-0.42 0.23-0.51 6-3-carene(t) o-terpineol(0.11%)
sabinene 0 .10 -0 .1
3 0 .1 0 -0.13 landrene(0.27%)
cr-phel methylsalicylale(0.14%)
cx-terpinene (0.13%) frans-dihydrocarvone (0.13%)
myrcene 1 .5 8 -1
.7 0 1 .5 5 -1.62 p-cymene(2.07%) (0.06%)
isodihydrocarveol
0-terprnene 0 .0 1 -0 .0 2 0 .0 1 -0.02 limonene(82.12%) decanal(0.15'l")
limonene 87.66-91.85 89.65-93.01 (Z)-B-ocimene (0.O4%) trans-caw eol (0.62'/.)
B-phellandrene 0.27 0.25-0.26 (E)-B-ocimene (0.06%) cls-carveol(0.34%)
(Z)-B-ocimene 0 .0 1 -0 .0 3 0 .0 1 -0.02 y-terpinene (0.10%) carvone(1.21o/o)
y-terpinene 0.02-0.03 0.04 acetophenone(t) linalylacetate(0.68%)
(E)-B-ocimene 0 .17 -0 .3 6 0.14-0.26 terpinolene (t) perillaldehyde (0.09%)
terpinolene 0.39-0.67 0.48-0.59 frans-linalooloxide- (0.02%) acetate(t)
cx-terpinyl
cx-p-dimethylstyrene (1.36%) geranylacetate(0.13%)
frans-linalooloxide- o.23-0.29 0.18-0.24 methylbenzoate(0.56%) methyleugenol (0.760/")
cis-linalooloxide. 0 .15 0 .13 -0.15 linalool(0.52ol.) benzylbenzoate(0.66%)
linalool 1.16-3.24 0.82-1 .97
linalylacetate 0.07-0.27 *correctisomernot identified
0.19-0.47
t = trace(< 0.01%)
B-caryophyllene 0.02-0.03 0.02
terpinen-4-ol 0 .0 7 -0 .1 0 0 .0 8 - 0.15 In comparison, the hydrocarbon fraction of this oil was
o-terpineol 0.48-0.66 0.40-0.55 found to contain:
nerylacetate 0.02-0.06 0.05-0.09 uthujene (t) y-terpinene
(0.31%)
0.09-0.21 0 .0 8 - 0.14 0-pinene(0.63%) a.6+^nhan^n6 /+\
geranylacetate 0 .15 -0 .1
8 0.22-0.26 camphene(0.28%) ct-p-dimethylstyrene(1.65%)
nerol 0 .1 2 -0 .1 7 0 .1 1 - 0.13 sabinene(2.61./.) linalool(0.10%)
geranrol 0 .0 1 -0 .2 3 0 .0 9 - 0.1
9 myrcene(1.84%) nonanal(0.05%)
6-3-carene(t) p-mentha-1,3,8-triene (0.03%)
nerolidol- 0 .0 4 -0 .1 0 0.07-0-12 o-phellandrene (0.08%) cis-limoneneoxide (0.05%)
farnesol* t-0.02 t-0.01 o({erpinene(0.12"/.) /rans-limonene oxide (0.14%)
*correctisomernot identified p-cymene(2.83o/o) terpinen-4-ol(0.02i")
t = trace(< 0.01%) limonene(88.79%) trans-dihydrocarvone(0.02%)
(E)-B-ocimene (0.18%) linalylacetate(0.15%)
330
fiili1
-ffifitllll
,,]lruuruluur^
spathulenol(0.21'/") santalol*(0.10%)
globulol(0.56%) (Z,Z)-Iarnesol (0.06%) Table ll. Amounts (in mg per 100 g of oil)
of oxygen heterocycliccompounds in Spanish
*correct isomer not identified
and genuine ltalianand ltalian lab-prepared
t = tra ce (< 0 .0 1 %)
bitter orange oils. (Number in parentheses
Finally, once the hydrocarbon fraction and the so-called refers to number of samples.)
oxygenatedfractionwere desorbedfrom the silicagel, Chouchi
et al. desorbedthe residue and it was found to be comorised Lab-
Spanish Genuine prepared
of the following constituents: oils oils oils
heptanal(0.22%) menthylacetate(O.57%) Compound (3) (6) (6)
sabinene(0.05%) cr-terpinylacetate(1.78%) osthol 366-371 159-184 99-192
5-methyl-6-hepten-2-one tetradecane(0.30%) 71 52-73 36-92
(0.04o/o) nerolidol.(028%) epoxybergapten 119-186
304-328 188-322
myrcene(0.49%) ledol( 1. 41% ) unknowncoumarin1 12-13 2-13 10-16
o-phellandrene (0.85%) spathulenol(0.29o/o)
o-terpinene(0.06%) globulol(0.38%) meranzin 307-332 7BB-1172 635-1403
p-cymene(0.56%) (Z,Z)larnesol(0.64%) isomeranzin 208-213 154-211 172-299
lim on en e(1 .16 % ) benzyl benzoate (0.83%) unknowncoumarin2 to- z + 20-35 20-53
(Z)-B-ocimene (0.06'/.) citropten(0.32%) tangeretin 95-99 59-156 66-122
(E)-B-ocimene (0.13%) methylpalmitoleate (0.16%) heptamethoxyflavone 23-25 5-14 3-21
y-terpinene(0.07%) bergapten(2.16'/.) nobiletin 76-Bs 54-151
34-87
frans-linalool oxide. (0.19%) isobergapten(0.09%) tetra-O-methylscutellarein 5-B 10-18 5-10
cr-p-dimethylstyrene (0.62%) suberosin(5.20%) unknowncoumarin3 48-57 39-50 24-36
2-nonanone(0.11%) auraptenol(2.81%)
linalo ol(1 .40 % ) isomeranzin(23.47%) epoxybergamottinhydrate 24-42 13-45 9-26
no na na (0.1
l 0% ) nonadecanal (0.70%) meranzinhydrate 18-39 10-62
p-mentha-1,3,8-triene osthol (4.24ok)
(0 .15 % ) 5-methoxyiso meranzine(0.08%)
cls-sabinenehydrate(1.25o/o) B-(3-methyl-2-oxobutyl)-7-
frans-limonene oxide (1.30%) methoxycou ma rin (0.22'/.)
size)Porasil.At 12 min, the llorvwas su'itchedto the second
terpinen-4-ol(0.40%) 8-(3-methylbutyl)-7-
c-terpineol(0.85%) methoxycoumarin (0.14%) column, a 25 cm x 4.6 mm (8 pm particle size)Zorbaxcolumn
frans-dihydrocarvone 6-(3-methyl-2-oxobutyl)-7- u'ith a pressureof 789psi and a column temperatureof 30'C.
(0.25%) methoxycoumarin (t) The UV spectra of eluting peaks were monitored in the
isodihydrocarveol (0.75%) meranzin hydrate(6.42%) region of 200-400nm. The oxygenheterocycliccompounds
frans-carveol (2.990/") meranzin(14.27%)
found in six genuine samplesof Italian bitter orange oil and
cis-carveol(2.21%) heptacosane(0.02%)
carvone(2.24%) tangeretin(2.75%) si-xlab-preparedbitter orange oils can be seenin Table II.
linalylacetate(2.06%) nobiletin(0.49%) As can be seen in Table II, meranzin was the major
comDonentof the Italian oils.The authorsnoted thnt the lab-
t = tra ce (< 0 .0 1 %) prepared oils did not contain any meranzin hydrate. They
Usins a combination of HPLC-MS and GC/MS after believed that this compound was formed during the indus-
,",r"r."d phase HPLC fractionation, Buiarelli et al. (1996) trial nrocess.
determined that the non-volatilefraction of bitter orangeoil Sevencommercial bitter orange oils r,verealso examined
contained the following constituents: for their oxygen heterocyclic compounds (Table III). The
authors concluded that these oils were adulterated r'vith
nobiletin auraoten products not containing an oxygen heterocyclic fraction
tetra-O-methylscutellareinbergamottin
tangeretin becausethe amounts found were considerablylower than
expected. They postulated that the adulterants may have
Also in 1996,Dugo et al. analyzedthe non-volatileoxygen been sweet orange terpenes or srveetorange oil. The pres-
heterocyclic fraction of bitter orange oils from a variety of enceof bergamottinand 5-(geranybxy)-7-n'iethoxycoumarin
sources.The authorsusednormal DhaseHPLC with two on- in samples6 and 7 indicated that the oil probably contained
Iine columns coupled together,a photodiode array detector either lemon or lime oil as adulterants.
and two mobile phases(A. hexane:ethylacetate,9:1 and B. A peel oil ofbitter orangeproduced in Italyrvas analyzed
hexane:ethylalcohol,9:1). They obtained injection volumes by Caccioni et al. (1998).Using GC to deterrnine the reten-
of 20 pL of oil samplesby diluting approximately50 mg of oil tion indices and quanitative data, and GC/MS to confirlrr
and 0.1 mL of a coumarin solutionof kfr6rvnconcentrationto component identities, the authors found that bitter orange
1 mL in hexane:ethylacetate(75:2,*).The elution program oil contained the following compounds:
usedwas: 0-2 min 987oL + 27oB : 2-25min from 9B7oA + 27o
othujene (t) B-pinene (0.33%)
B to SEoA + 957oB ; 45 -50 min fronl' 57oA + 957oB to 98% (0A0%)
cx,-pinene octanal(0.08%)
A+ 27oB. The flowrate usedwas1.6ml/minwith apressure camphene(t) myrcene(1.BB%)
from 0-12 min though the 30 cm x 3.9 mm (10 pmparticle sabinene(0.08'/.) (0.02%)
cr-phellandrene
331
Table lll. Amounts (in mg per 100 g of oil) of oxygen heterocyclic
compounds in seven adulterated bitter orange oils
Compound 1 2 3 4 5 6 7
bergamottin + +
5-(geranyloxy)-7-methoxycou
marin + +
osthol 114 10; 10; 117 113 140 197
bergapten 37 39 31 34 31 27
epoxybergamottin 127 100 72 70 84 60
unknowncoumarin1 B 6 7 A 7 A
1;
meranzin 401 314 122 tJ3 205
isomeranzin 110 116 77 90 69 126 108
q
unknowncoumarin2 8
tangeretin 78 70 72 53 62 53 34
heptamethoxyflavone 25 32 24 30 27 4
nobiletin 4b 45 J+ 40 33 18 to
tetra-O-scutellarein 31 18 22 to 7
unknowncoumarin3 4 4
epoxybergamottin hydrate 26 34 3B 32 4; 24 24
meranzinhydrate 53 73 55 32 96 31 9B
+ oresence.actualamountnot determined
6-3-carene(0.01%) nerol(0.06%)
limonene(94.27%) neral(0.03%) A. Mosandl, U. Hener, P. Kreis and H. G. Schmorr,Enantiome4c
(Z)-B-ocimene (t) ger aniol( 0. 11% ) distribution of a-pinene, ftpinene andlimonene in essential oils
(E)-B-ocimene (0.23'/.) perillaldehyde (0.03%) and extracts.Part L Rutaceaeand Graminae.FIav. Fragr. J., 5,
y-terpinene(0.O2'/") ger anial( 0. 11% ) 193-199(1e90).
octanol(0.33%) decanol(0.05%) M-8. Huang, D-X. Zhang, C-T. Yan and S-B. \ang, ldentification
oxidet (t)
crs-linalool cr-terpinylacetate(0.03%) and deter-mination of the constituents of es,sentialoil extracted
inalool6x;flsr (Q.05o/o)
trans_l neryl acetate(O.04'/.) fromFructus Citriaurantii by GC andCCIMS. Sepu,8,321-325
terpinolene(0.O2%) dodecanal (0.01%) (leeo).
linalool(0.78%) decylacetate(0.02/") L. Mondelio, P. Dugo, K. D. Bartle, G. Dugo and A. Cotroneo,
terpinen-4-ol(0.06%) B-caryophyllene (0.07'/.) Automated HPLC-HRGC: Apouerful methodfor essentialoil
orterpineol(O.26%) F-cubebene+ (0.05%) analysis. Paft V. Identification of teryene hydrocarbons of
decanal(0.11%) B-elemene+ (0.01%) bergamcft, lemon, mandarin, sraeet orange, bitter orange,
octylacetate(0.05%) (E)-nerolidol (0.07%) grapefruit, clernentine and Merican lime oils by coupled
t presumablyfuranoidform HPLC-HRCC-MS0TD). Flav. Fragr. J., rO, 33-42 (1995).
t incotrectidentiticationbased on elution order
t = tra ce (< 0 .0 1 %) L-F. Zhn, Y-H. Li, B-L. Li, B-Y. Lu and W-L. Zhang, Aromatic
plants and essential constituents (supplement l). South China
In 1999,Sawamuraet al. analyzedtwo oils of C. aurantium Institute of Botany, Chinese Academy of Sciences,Hai Feng
produced in Japan.The constituentsidentified in these oils Publ. Co. distributed by Peace Book Co., Ltd., Hong Kong
( 1995).
were as follows:
cr-pinene(0.5-0.6%) linalool(0.1-0.2%) O. Bussaada,Yariation of essential oil yield and composition of
(0.7-0.9%) neral(f0.1%) Citrus aurantium var. alnaro M. Sc. thesis, Mediterranean
B-pinene
myrcene(1.6-1.7o/") cr{erpineol(t-0.1o/o) Agronomic Institute, Chania, Greece (1995).
limonene(92.O-94.7%) geranial(t-0.1%) D. Chouchi, D. Barth, E. Reverchonand G. Della Porta,Bigarade
T-terpinene(0-0.1%) geranylacetate(0.1%) p eel oil fracti onat i on b y supercritical carbon dioxide d eso wt i o tt.
terpinolene(t) citronellol(0-t) J. Agric. Food Chern.,44, f 100-1f04 (1996).
octanol(0.1-0.2%) nerol(01) F. Buiarelli, G. P. Cartoni, F. Coccioli and T. Leone, Anahlsi,sof
decanal(0.1%) geraniol(01)
bitter essential oils from orange and grapefruit by high
t = tra ce (< 0 .1 %) performance licluid chromntographq r,aith microbore columns.
j. Chromatogr.,730, 9-16 (1996).
T. N amba, I. Araki, M. Mikage and M . Hafion, Fundament al studi es
on the eaaluation of crude drugs YIII. Monthly aariations in P. Dugo, L. Mondello, E. Cogliandro,A. Verzeraand G. Dugo, Orz
anatomical characteristics and chetnical corryonents ofthe dried the genuinenessof Citrus essential oils. Sl.Oxygen heterocyclic
compoundsofbitterorange oil(Citrus aurantium). J. Agric. Food
fruit peels of Cltrus unshiu, C. aurantiurn and C. natsudaidai.
ShoyakugakuZasshi,39(1), 52-62 (1985). Chem., 44, 544-549 (1996).
S. Inoma, Y. Mry"gr and T. Akieda, Characterization of Citrus oil D. R. L. Caccioni, M. Guizzardi, D. M. Biondi, A. Renda and G.
(mainly orange oil, mandarin oil, tangedne oll), Kanzei Chuo Ruberto, Relationship betueen aolatile component,sof citrus
Bunsekishoho,29, 87-97 (1989). fru.it essenti.al oils and antimicrobial action on Penicilliurn
332
d.igitatunt and Penicillitnn it a/lar rit. lnternat. j. Food NIlcrobiol.,
43. 73-79(1998). Table V. Percentage composition of some Artemisia
afra oils produced in Zimbabwe (W=derived f rom
NI. Sau,amura,S. H. Sun, K. Ozalcl, f. Ishikarva and H. Ueda,
wild plants; C-1,2,3=differentregions of Zimbabwe)
lnhibitonl fficts of Citnts essettitil rtilsantl tLtcirconponentson
tlte.fonnationo.fN -nitrcsotlinrcthtllantine.!.Agric. Food Chem.,
47,4868-4B72(1999). Compound W-1 c-l c-2 c-3
tricyclene 0.1-0.2 t 0-0.2 0-0.3
Artemisia afra Oil c-pinene+ othujene 0.4-1.1 0.3 .1
0.5-1 0.7-1.8
Graven et al. (1990) analyzedtlie oils producecl from r.vild sJenchene 0.2-1.0 1.4 .1
0.4-1 0- 0. 6
camphene 0,3-3.9 8.0 0.6-3.8 3.0-5.6
populations of Aftentisia afra lacq. (South African \vomr-
B-pinene 0.1-0.7 0.4 0.2-3.7 0.3-1.5
r.vood)collected in the eastern cape of South Africa. Thev sabinene 0.1-2.6 0.2 0.2-0.5 0.6-7.9
founcl that the major componentsof the oils of 20 different myrcene 0.1-1.1 1.6 0-0.5 0. 6- 1. 1
genotlpes ranged trs {bllou's: (X-terprnene 0 . 1 - .11 0.3 0-1.8 0. 3- 1. 1
dehydro-1,8-cineole 0.1-0.2 0.1 1-0.7 0.2-0.7
1,8-cineole
(4.16-50.14%) B-thujone(1.16-65.04%) lrmonene 0.1-0.5 0.9 0.1-0.2 0-0.5
crthujone(4.72-75.60%) camphor(0-27.92%) 1,8-cineole 0 . 1 - 2 7 . 9 10.7 10.9-1
6.9 23.5-28.7
(E)-B-ocimene 0.1-0.3 t 0-1,0
y{erpinene 0.3-1.9 0.7 0-0.6 0.2-2.6
The 20 oils canbe groupedirito the {bllor.vingclien,otwes:
p-cymene 0.3-2.0 0.8 .6
0.6-1 1.2-1.3
s-thujone
> B{hujone> camphor > 1,8-cineole
(7) terpinolene 0 . 1- 0 . 5 0.3 0-0.2 0.3-0.5
cr-thujone
> B{hujone> 1,8-cineole
> camphor(5) artemisia
ketone 6.3-14.9 0.1 32j -3 4. 8 0. 1- 0. 3
> 1,8-cineole
o,-thujone > B{hujone> camphor(5)
santolina
alcohol 3 . 1- 10 . 1 - 2.5-8.0 0.1
othujone 1.0-2.9 0.7 0.2-4.9 0.1
o-thujone
> camphor> B-thujone> 1,8-cineole
(1) anemisylacetate t-0.1 - 0-0.9 0-0.2
> camphor
B-thujone > d-thujone> 1,8-cineole
(1) pthujone t - 0-0.2 0-t
1,8-cineole
> camphor > o-thujone
> Bthujone(1) crs-sabinenehydrate 0.2-0.5 0.4 0-0.2 0.8-1.3
artemisia
alcohol r-0.3 - 0-0.1 0-0.1
Six vears later, Worku and Rubiolo (1996) examinedthe campnor+ 0-copaene 8.5-27.1 50.3 21.8-24.420.2-21.3
changes iri rnajor component composition of A. afra orl frans-sabinenehydrate 1.8-4.4 3.5 0.1-3. 7
produced from fresh trnddried Ethiopian plantshanrestedat cls-p-menth-2-en-1
-ol 0.2-0.4 0.8 0-0.5 0.9-1.s
different stagesof maturity The results of this study are
hnrnvl a^airlo 0" 3-1.5 0.5 0.2-0.7 1.6-3.3
B-caryophyllene 0.5-2.3 1.2 0.4-0.7 2.0-5.0
shor'vnin Table I\i -
terpinen-4-ol r-0.1 0-0.1 0.3-0.7
In 1999, Mangena and Muyima reported that an oil of myrtenal - 0-0.1 0.3-0.6
A. ofro produced frorn plants collected in the eastern trans-p-menth-2-en-1 -ol 0.2-0.3 - 0-0.2 0.2-0.4
cape region of South A{i"ic:rpossessedthe follorving mLtjor 6-terpineol 0.1-2.5 0.7 0-0.5 0.9-1.0
constituents: borneol 0.6-3.4 2.8 0.8-1.4 14.2-17.0
c,terpineol 0.1-0.7 0.4 0.2-2.4 0.2-1 .9
(8 .19 % )
1 ,8-cine ole ( 13. 13% )
B- t hujone bicyclogermacrene 0.2-0.s - 0-0.8 0-0.2
cr-thujone(78.68%) piperitol. 0.1-0.7 1.8 0-0.6 0-0.1
E-cadinene 0.5-0.8 0.2 0.6-1. 2 1. 6-. 19
Also in 1999, Chagondaet al. annlyzedthe oils of A. cLfra cuminaldehyde f0.5 0.2 0-0.7 t-0.2
produced fron'r pltrnts that lvere harvestedin the rvild and myrtenol r-0.1 0"3 0-0.1 0.2
{r'om cultivated plants in Zimbabrve. The results o{'this calamenene. 0.1-0.9 0.1 0-0.1 0.1-0.4
comparativestudy are shorvnin Table V. F-romtheseresults, cls-carveol 0.1 0-0.1 r-0.1
caryophyllene oxide t-0.1 0.1 0-0, 1 0. 1
it can be concluded that the comoosition of Zirnbabu,eanA.
methylilnolenate t-0.1 0-0.1
cLfraoilisdifierent fr:ornthat reported fol SouthAfrican oiis. germacrene D-4-ol 0.1 - 0-0.1
p-cymene-B-ol 0.1 0-r 0-0.1
spathulenol - 0-0.6 0-0.2
T-muurolol t-0.5 0.4 0-0.6 0-0.2
Table lV. Percentagecomposition of the major intermedeol t-0.4 0.1 0-0.3 0.1-0.2
components ol Artemisia afra oil produced from a camphoris majorcomponentin this mixedpeak
plants harvested at different maturity stages * correctisomernot
identified
t = trace (< 0.1%)
Vegetative Budding Full flowering
stage stage stage
According to the authors, this is an example of tr,vomore
Compound Fresh Dried FreslT Dried Fresh Dried chemotlpes,such as:
santolinatriene 6.0 4.0 5.8 5.8 8.0 7.3 Type 1: artemisiaketone> camphor> 1,8-cineole
yomogialcohol 26.8 23.6 24.7 23.7 24,6 21.6 fype 2:1,8-cineole > camphor> borneol
1,8-cineole 7 .2 8.4 7r3 7.B 7.8 7.6
artemisylacetate 24.4 32j 27.5 29.9 28.2 29.9 H. Graven, L. Webber, M. Venter and J. B. Gtrrdner'.flic
2-phenethvlacetate 2.1 2.3 2.4 3.9 2.0 2.3 dereloynrcnt of Afternisia afra Jucq. as a nerc essentittl oil t rttp
J. trssent.Oll Res.,2, 215-220(1990).
333
T. Worku and P. Rubiolo, Major constituents of Aftemi,sia afra oil.
Table Vl. Chemicalcomposition (%) of palmarosaoil
J. Essent.OilRes., 7,355-357(1996).
produced from healthy plants compared with oils
T. Mangena and N. Y. O. Muyima, Comparatiae eaalaation of the
produced from chlorotic plants
antimicrobial actiaities of essentialoik of Art emisiaafra, Pteronia
incana and Rosmorinus fficinalis on selectedbacteria and Eeast
strains. Letters Appl. Microbiol. 28, 291-296 (1999). Partially Severely
Healthy chlorotic chlorotic
L. S. Chagonda, C. Makanda and j. C. Chalchat, The es,sentialoil of Compound plant oil plant oil plant oil
cultioaterl Artemisia afra Jacq.from Zimbabu;e. Flav. Fragr. J.,
14. 140-142(1999). saotnene 0.1
myrcene 3.3 3.6 2. 9
PalmarosaOil o-phellandrene 0.1 0.1 0. 1
0-terpinene 0.1 0.1 0. 1
In 1989,Sethi et al. analyzeda number of palmarosaoils and
limonene 0.3 0.3 o. 2
found that they contained the following components: (Z)-B-ocimene 0.9 1.0 0. 8
cr-pinene(t) geranylacetate(5-20%) (E)-B-ocimene 2.0 1.9 t.o
334
geranylformate(t) 7-epi-a-santalene(t)
geranylacetate(10.1%) geranylbutyrate(0.1%) Table Vll. Comparative percentage composition
B-elemene (0.1%) (E)-nerolidol
(0.1%) of ginger oil and its extracts
B-caryophyllene (1.2o/") caryophylleneoxide (0.2%)
(0.1 % )
o-h umu len e (E,E){arnesol (1.9%)
Compound SFE oil Sox
o-selinene(0.1%) (E,E)-farnesylacetate(0.1%)
germacreneA (t) 1,8-cineole I tt
linalool I tt
borneol 0.60 0.38 0.67
K. L. Sethi, M. L. Maheshwari and R. Gtpta, Genetic dioersity and C)[terpineol 2.51 0.22 1 .1 2
deaelopmentof high oil y ieldingp almnrosa strains. h: Proceeclings
Tlth lntemational Congress of E,s,sentialOils, Fragrances aid Iinalylacetate 0.80 0.25 0.68
Flaaours.Edits., S.C. Bhattacharyya,N. SenandK. L. Sethi,Vol. eugenol 0.83 0.10 0 .9 7
3, 89-96, Oxford and IBH Publ. Co., New Delhi (1989). B-caryophyllene 0.31 0.11 2 .2 8
nerylacetate 0.64 0.16 0 .6 7
N. Siddiqui and S. C. Carg, Chemical composition tf Cymbopogon
martinii (Roxb.)Wats.var.mat'tinii. j. Essent.Oil Res.,2,93-94 ar-curcumene 10.87 11"08 1 3 .2 0
(1ee0). zingiberene 24.70 35.46 30.70
bisabolene* 3.53 4.50 3.50
E. V. S. Prakasa-Rao,R. G. GaneshaRao and S. Ramesh,Changes
in content and composition of som.ees,sentialoil due to pottibln B-sesquiphellandrene 6.81 B.B7 8.50
d,eficienciesof phosphotus and potassium in a red soil region of B-farnesene* 14.17 23.62 16.40
Bangalore. PAFI I., l8(1), 25-27 (1996). B-selinene I 0.55 0.32
M. Lis-Balchin, S. Deans and S. Hart, Bioactioitr1 of Neto Zealand (Z,Z)larnesol I 0.60 0.49
medicinal plant essentialo ils.In: Proceetli ngsI ni. iyryt. Medicinal (E,E){arnesol 0.88 1.46 0 .7 1
Aromatic Plants. F,dits., L. E. Craker, L. Nolan and K. Shetti, cubenol 1.15 1 .7 4
Acta Hort., 426, 13-30(f996). grngerone z-zo 0.53 1.18
B. R. R.ajeswaraRao,P. N. Kaul,A. K. Bhattacharya,G. R. Mallavarapu eudesmol* 1.31 1.08 1 .4 6
and S. Ramesh,Yield and chemical composition of the essential nerolidylacetate 2.21 1.56 2 .0 5
oils of three Cqmbopogon speciessuffering from iron chlorosis.
bisabolylacetate* 1-82 0.45 1 .1 4
Flav. Fragr.I., 11,289-293(1996).
lanceolylacetate" 0.54 r 0.76
H. K. Srivastava and G. K. Satpute, Induction of mutations for gingerol 6.02 - 2.28
enhanced essential oil in palmarosa (Cymbopogon mar-tinii). shogaol I z .z z _ 2.29
J. Essent.Oil Res.,10, 287-29f (1998).
Oil = hydrodistilled
oil
P. C. Sarma,P. Baruah,M. G. PathakandP.B. Kanjtlal,Comltarison SFE = supercriticalfluidextract
of the major conxponents of the oils of eight selections of Sox = soxhletextract (solventnot noted)
Cymbopogon maftirtii (Roxb.) Wats. var. maftinii. J. Essent. Oil ' correctisomernot identified
Res.,lO, 673-674(1998). t = trace(< 0.01%)
335
B-elemene (0.9%) (4.7%)
B-bisabolene
aromadendrene (0.5%) 1^t^^^^6^+
u^ ,- t a t
11 AO/ \ Table Vlll. Comparativepercentagecomposition of
I tEDvt t9 \ / .a /o,/
336
B-elemene (0.147") nerolidol.(1.01%) This oil is not typical of a ginger oil used in commerce.In
0-bergamotene-(0.03%) B-eudesmol(0.52%) -
(E)-B-farnesene(0.18ol.) fact, {rcm the compositionrepoited, it appearslike itwas not
heptadecane (0.36%)
allo-aromadendrene (0.08%) octadecane(0.08%) dlstllled long enough.
ar-curcumene (3.52%) nonadecane (0.09%) This sameyear,Yu et al. (1g98)used GC/MS to comDare
(0.05%)
B-selinene dibutylphthalalsrfI (e 01o/o) the
y-cadinene(O.79%) hexadecanoicacid(0.02"k) _compositionof ginger oil producecl by clistillation and
cold-pressingrvith that of a supercriticalfluicl COo extractof
B-bisabolene(2.70%) eicosane(0.08%)
elemol(0.02%) ginger. The results of this study are shown in Tabie X.
heneicosane (0.07%)
In 1999,Li used GC/MS to analyzean oil produced from
- correct isomer nol identified ginger rhizomes grown in Guangxi. The oii rvas found to
t should be 6-methyl-5-hepten-2-one
+ furanoidforms conl ai nfhe l bl l ow i ngt.onsifuenti
i :
rrr impurityleached from plastic
337
cr-pinene(2.37%) o-copaene(0.65%) M. Taveira Magalhaes,M. Koketsu, S. L. Gongalves,F. R. Duarte,
camphene(4.40%) B-elemene(1.25'/4 R. L. de Oliieira Godoy and D. Lopes,Brazilian ginger: general
sabinene(0.30%) ar-curcumene (13 77'/.) asx)ects, essential oil and oleore sin.Vart 7. C eneral aspects of the
B-pinene(0.69%) zingiberene (20.05%) essentialoil. Cienc. Technol. Aliment., 17, 64-69 (1997).
1,8-cineole (4.19'/") (Z)-bisabolenea V .67%) M. Taveira Magalhaes,M. Koketsu, S. L. Gongalves,F. E. P.
terpinen-4-ol (1.13%) (E)-B-farneseneb (12.90%) Comej o and L. M. R. M arques,B razilian gin ger: general aspects,.
borneol(1.88%) elemol (6,22"k) essential oil and oleoresih. Part 2. Drying, essential oil and
o {e rpin eo (1.8
l 1% ) cr-eudesmol(2.83%) oleoresin.Cienc. Technol. Aliment.. 17, 132-136(1997).
neral(6.63%) B-eudesmol(3.94%) Z-Q.Li,M. Luo, G-Y. Ma, Y-Q. Zhangand G-J.Zhao,CC/MS study
geranial(4.61'/.)
on chemical constituents from Zingiberaceae plants. Guangpi
u should be 9-bisabolene
Shiyanshi, l4(1), r-5 (1997).
b should be p-sesquiphellandrene P. S. Variyar, A. S. Gholap and P. Thomas,Effect of yirradiation on
the aolatile oil constiiuents offresh ginger (Zingiber officinale)
L-F. Zhu, Y-H. Li, B-L. Li, B-Y. Lu and W-L. Zhang, Aromatic
rhizome. Food Res. Internat., 30,4f-43 (1997).
plants antl essential constituents (Supplement l). South China
Institute of Botany, Chinese Academy of Sciences,Hai Feng H-L. Zhou, L-X. Wei and H-M. Lei, Analysi's of oolatile oil from
Publ. Co. distributed by Peace Book Co', Ltd., Hong Kong rhizorLe zingiberis by GC /MS . Zhongguo Zhongrao Zazht, 23,
( 1 99 5). 234-236(1998).
M. D'Alpaos, P. Traldi, G. Tassinato and P. Pallado, Extraction of Z. Yu, H-M. Wu and J-K. Ding,The oolatile chemical componentsof
(
esseitial oilsandJlauorsuith classicand supercritical technique's: fr eshZingib er ffi cinale. ActaBot.Yunnan,20(-l), I I 3- 1I 8 1998).
o comparison.RivistaItal. EPPOS (Numero Speciale- Agosto), S-Y. Li, Analgsis of oolatile oil in ginger by CC/MS Guangxi
200-207(1997). Huagong,2B(l), 48-49 (1999).
P. Pallado, G. Tassinato, M. D'AIpaos and P. Traldi, Gas chromato--
graphq/mnssspcclromelrqin 0r('mochemistry:a comparisonoJ
nss)ntialoilsdnd flaror's irtractel by classicnland supercrilical
techniques.Rapid Commun. Mass Spec.11, 1335-1341(1997).
338