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Progress in Essential Oils

& Flavorist,
fromPerfumer
Reprinted 1995,Vol.20, No.1, P. 47
JanuarylFebruary

RosemaryOil This sameyear Kreis et al. (1991) subjecteda nun'rberof


In 1988,Bayrak and Akgul examinedthe compositionof oils samplesof rosemaryoil to thin-layer chromatographicisola-
produced from rosemary collected from three different ti on of the borneol /i soborneol fracti on which was
locations in Turkey. The method of analysischosen by the stereoanalyzedafter solvent extraction on a permethylated
authorswas GC/MS. A summary of the results of this study B-cyclodextrinchiral GC column. A secondsampleof four of
can be seen in Table I. the oils was initially treated with LiAlH4 to release the
In 1991, Cioni et al. compared the composition of lab- alcohols bv reductive cleavage,after which it was analyzed
distilled oils of rosemaryproduced from dry and fresh pltrnt first by TLC and then chiral GC asnoted above.Of the seven
material. The results of this study are found in Table II. In samples analyzed,the enantiomeric ratios of borneol and
addition, the authorsalsocomparedthe amountsof selected isoborneolwere found to be:
constituents in an oil produced from plant material har- (1R,2S,aR)-(+)-borneol
(2.2-1
5.4"k):
vested in the vicinity of Pisa (Italy) with oils produced {rom (1S,2R,45)-(-)-borneol
(84.6-97.8%),
a variety of different origins. These results can be seen (1S,25,aS)-(+)-isoborneol*
(46.2-7
0.9%):
(1R,2R,4R)-(-)-isoborneol*
(29.1-53.8%)
compiled in Table III.
Also in 1991,Jainet al. showedthat oilsproduced from 40- The enantiomeric distribution of borneol isolated from
dav old shoots that rvere produced in vitro contained the the bornyl acetateof the four samplesof rosemaryoil ana-
expectedorygenatedmonoterpenoid components.The au- lyzed was found to be:
thors further shor,vedthat the oil of one-year-old,in-vitro- (1S,2R,45)-(-)borneol
(97.4-99.3%):
rtrisednlants was almost identical to an oil obtained from (1R,25,R)-(+)-borneol
(0.9-2.6%)
one-year-old,field-grown plants (seeTable IV). In 1992, Svobodaand Deans examinedthe variability in
the voiatilesof varioussamnlesof rosemarvthat are available
Table L Chemicalcomposition (o/o) on the British market. Initially. the authois reported that 35
of Turkish rosemaryoil tons of dried rosemary is imported into the UK annually
along with 80 tons of rosemary oil. Svoboda and Deans
Compound Alanya* Aydin Sinop obtained eleven (eight Spanish, two Moroccan and one
t 0.27
unknown) commercialrosemarysamplesandcomparedthem
cr{hujene 0.43
0-prnene 9. 61 4. 18 11.47
campnene 4. 99 9.25 5 . 15 Table ll. Comparativecomposition (%) of rosemary
B-pinene+ sabinene 2.02 1. 77 1.93 oil produced from fresh and dry plant material
myrcene 0.98 1. 90 0.61
c-phellandrene I Gompound Fresh plant oil Dry plant oil
lrmon en e t-t3 1. 49 1.01
cr-pinene 26.18 28-91
1 ,8-cine ole 40-57 40.38 18.16
campnene 3.95 4.1 3
,tsterpinene t I 0.52 B-pinene 2.42 1.6 2
p-cymene 1"10 1. 22 0.93 myrcene 1.19 1.9 4
:inalool 0.80 1. 48 0.73
limonene 2.32 2.55
campnor 14.57 20.04 23.06
1,8-cineole 24.79 1 7 .5 0
anrn\rl rn6+r16 3. 85 0.75 t y-terpinene 0.87 0.69
:erpinen-4-ol 1. 80 1. 71 1.18 p-cymene 0.90 1.3 4
3-caryophyllene
campnor 6.85
+ unknown 1. 82 1. 91
linalool 2.93 2.3 5
.r-terpineol 2. 13 2.49
bornylacetate 0.74 O.BB
: crne ol 5. 63 9. 19 11 . 1 5 B-caryophyllene 1.35 t .Jz

, erbenone 0.93 15.58


a-terpineol 6.50 6.22
,r.-nUmUlene t 0. 29 0.53
borneol 5.80 B.5B
,:.-copaene 0.22 t t
verDenone 0.35 0.42
= :'a ce (<0 .0 1 %) geranrol 1.07 1 .4 7
-: - =- ^^ T, , - t , ^, ,
dJ ^
|| | u|^gy
Table lll. Percentage amounts of selected Table lV. The oxygenated constituents (%)
components of various rosemary oils found in rosemary oil produced from
in vitro-proliferated shoots, in vitro-raised
Oilorigin u-pinene verbenonecamphor borneol 1,8-cineole potted plants and field grown plants

France 12.5 25.0 6. 3 18.5


In vitro shoot ln vitro plants Fieldgrownplants
Corsica 24.0 27-0 3 .0 2. 0 6.0 Compound (40days)oil (1 year)oil (1 year)oil
Italy 10.0 I 1 1 .0 6.3 44.0
1,8-cineole 4.6 5.0 5 .0
Sardinia 32.0 I 4. 0 15.0
Morocco 12.0 t 1 5 .0 5.0 40.0 camphor 15.2 25.5 25.7
T un isia 1 1.0 2 .0 1 0 .0 7.3 48.0 linalool 2.3 5.0 4 .2
Spain 22.0 3 .0 tI.3 3.0 23.0 bornylacetate 26.8 9.5 9 .6
Portugal 12.0 I 9 .0 t 14.0
terpinen-4-ol 6.2 5.0 3. 1
Algeria 26.0 22.0 8 .0 4. 0 t
Yugoslavia 22.O I ' 1 3 .0 7.0 32.0 5.2 5 .5
Greece 23.0 I 7 .0 t 28.0 borneol 8.6 10.5 1 0 .5

t = trace (<0.1%) verbenone 5.2 5.2

with a samplewhich they grew and dried in Scotland.


They found that the oil contents varied from 1.0- Table V. Comparative chemical composition (%) of rosemary
2.37o while the main components varied as follows: oil produced from different localities in Spain
cr,-pinene(6.7-20.2%) camphor(15.1-25.9%)
camphene (3.8-8.9%) (1.9-8.6%)
borneol Socovos-
(18.4-41
1,8-cineole
Compound Carrascoy
Almendricos
Moratalla Socovos Sorbas
.6%\
In addition,the authorsalsodeterminedthevaria- u-thujene 0.39 o.41 0.83 0.27 1 .0 6
0-prnene 23.20 23.18 20.53 21.13 20.07
tion in the same major component in oils obtained campnene 10.10 11.29 9.18 8.12 2 2 .2 8
from a variety of commercial sources.The variation B-pinene 4.92 5.75 5.06 4.90 3.O2
was found to be as follows:
sabinene 0.33 0.32 0.31 0.31 0 .0 6
(3.1-28J%)
cr-pinene camphor(10.3-27.9o/o) 6-3-carene 0.37 0.01 0.01 0.04 0.03
camphene(4.2-10.7o/o) borneol(2.9-4.3%) myrcene 1.96 0.89 1.11 1.49 0 .0 9
(8.5-2B.6%)
1,8-cineole cr-phellandrene 0.50 3.94 3.52 4.45 0.82
An oil produced from an oleoresin was fairly d,-terpinene o.42 0.43 0.40 0.63 1 .6 2
tlpical except that the borneol content was greater limonene 3.56 4.26 3.84 4.23 4.04
Ih a n any olt he oils .e .g .: 1,8-cineole 12.45 14.13 20.78 25.29 6.11
(Z)-B-ocimene 0.09 o.41 0.17 0.47 1 .8 3
c-pinene(19.3%) camphor(14.6%)
camphene (7.2o/") y-terpinene o.57 0.90 0.79 1.66 2 .0 6
borneol(5.5%)
(26.9%)
1,8-cineole (E)-B-ocimene o.29 0.38 0.02 0.07 0 .1 5
p-cymene 2.57 2.40 2.04 1.29 5 .7 4
Also in 1992,SanchezGomezetal. comparedthe
terpinolene 0.30 0.68 0.55 1.29 0 .3 4
chemicalcompositionofrosemaryoil produced from
plant materials harvestedin different parts of Murcia campnor 9.30 14.27 10.94 B.B5 16.07
linalool 0.36 0.56 0.52 0.58 0 .16
andAlbacete(Spain).The resultsofthis comparative bornylacetate 0.52 0.22 1.43 0.93 1 .5 1
study can be found in Table V B-caryophyllene 0.93 2.07 3.09 2.78 1-37
A year later, Catalanoet al. (1993) compared the
terpinen-4-ol 0.39 0.79 0.74 0.54 0.61
chemical composition ofoils obtained from the leaves/ cr-humulene 0.26 0.68 1.15 0.83 0.48
flowers, branches/stemsand the entire rosemary sterpineol 2.71 o.02 1.20 0.90 0.04
plant grown in Italy. The results of this study are borneol 6.92 3.83 4.69 2.79 2.31
found in Table VI. verbenone 4.87 0.07 0.09 0.02 0 .1 7
Cioni et al. (1993) compared the oil yield and 8-cadinene O.14 0.03 0.13 0.15 0 .1 8
composition of the oil produced at different harvest- caryophyllene oxide 1.44 0.07 0.06 0.34 0.03
ing times. Their resultsare summarizedin TableVIL
This same year (Anon 1993), a sample of Spanishrose- o-pinene+ crthujene(18.0%) isofenchone (0.3%)
mary oil was analyzedusing a combination of Kovats indices camphene(8.8%) camphor(16.0%)
on two difl'erent capillary columns and GC/MS. Using the B-pinene(5.5%) linalool(1.3%)
myrcene(1.6%) bornylacetate(2.0olo)
data presented for the oil on the polar column, the compo- limonene(7.3%) (0.3%)
terpinen-4-ol
nents identified and their amounts can be seen as follows: 1,8-cineole(25.0%) B-caryophyllene(0.4%)
French and Moroccan origins can be seenin Table VIII. In
Table Vl. Comparalivechemical composition (%)
contrasttwo samplesof Spanishrosemaryoil possessedthe
of various rosemary oils
following constituents:
Entire Leaves/ Branches/ cI-pinene (19.4-24.7o/.) (E)-B-ocimene (0.2-1.5%)
Compound plantoil flowersoil stemoil c a m p h e n e( 8 . 9 - 1 1 . 3 %) p-cymene(1.8-2.0%)
cI-prnene 24.50-27.72 25.84-32.58 6.96-7.57 B-pinene(2.2-3.4%) terpinolene (0.4-0.5%)
sabinene(0.0-0.4%) camphor(16.3-18.9olo)
campnene 5.73-6.91 5,54-7.53 2.03-5.22
6-3-carene(0.0-0.3%) l i n a l o o(l0 . 7 - 1 . 1 %)
B-pinene 2.04-2.31 2.14-2.43 0.85-1.39
myrcene(4.4-4.9o/o) bornylacetate(0.9-1.1%)
myrcene 2.40-2.88 2.22-3.38 0.85-0.95
a-terpinene(0.0-0.7%) B-caryophyllen e (1.4-2.4'/')
limonene 2.94-3.71 3.02-3.67 1.83-2.21 limonene(3.1-3.6%) terpinen-4-ol(0.5-0.7 %)
1,8-cineole 7.66-17.31 9.23-17.91 4.63-9.20 1,8-cineole (19.0-21.8o/o) lavandulylacetate(0.0-0.8%)
Y-terpinene 0.44-2.07 0.50-1.27 0.18-1.42 y-terpinene (0.6%) borneol(1.4-4.5%)
p-cymene 0 .73 - 1. 01 0. 70- 0. 82 0. 95- 1. 2 1
camphor 8.25-8.94 7.01-9.08 6.61-7.88 Lawrence and Shu (1993) reported that rosemary oils
linalool 2.81-4.27 2.57-3.32 2.46-3.25 from different origins could be differentiated by their varia-
bornylacetate 1.75-3.30 1.26-3.57 1.76-2.83 tion in selectedmajor components.The differencesbetween
B-caryophyllene 1.03-1.44 0.91-1.00 1.07-1.17 the various oils are shown in Table IX.
o,-terpineol 1 .09 - 1. 75 1. 12- 1. 98 0. 81- 1. 3 4 Also in 1994, Soliman et al. aralyzed two samples of
borneol 5.00-8.87 4.56-5.67 16.51-20.48 rosemary oil that were produced from plant material har-
verbenone 5.57-6.91 6.61-6.95 0.23-0.65
vestedfrom two different areasin Egnt, where it was under
geraniol 0.73-1.13 0.52-1.22 1.06-2.56
cultivation. The oils, which were analyzedby GC/MS, were
oil content (%) 0.53-0.71 0.66-0.90 0.02-0.05 found to contain more than 40 constituentsascan be seenin
Table X.
Also in 1994,Perrucci et al. used reten-
Table Vll. Chemicalcomposition (%) of the oil of rosemary produced tion indices to characterizethe composi-
from fresh and dry plants harvested at different times of the year in ltaly tion of a rosemaryoil that wasproduced in
the laboratory by a modified Clevenger
Harvest time procedure using plant material that was
September November harvestedin Italy. The compoundsidenti-
Compound fresh dry fresh dry fresh dry lresh dry fied in the oil were:

c[-prnene 13.61 24.50 25.78 30.67 11.98 22.85 25.25 27.72 o-pinene(30.67%) camphor(6.35%)
campnene 4 .02 6. 91 6. 13 7. 01 7. 28 4.72 5.29 5.73 camphene(7.01o/o)linalool(2.69%)
B-pinene 1 .95 2. 04 4. 59 3. 61 2. 07 1.17 2.76 2 . 3 'l B-pinene(3.61%) bornylacetate(4.43%)
myrcene 2 j3 2. BB 2. 75 3. 15 4. 70 3.45 1.84 2.40 myrcene(3.15%) B-caryophyllene(0.97'/.)
limonene(3.83%) (0.99%)
cxterpineol
limonene 1.94 2.94 2.74 2.83 4.47 3.55 3.56 3.71 (1'1.04o/o) borneol(2.04%)
1,8-cineole
1,8-cineole 5.32 7.66 12. 81 t 1. 01 8.97 6-77 19.81 17.31 y-terpinene(0.67%)verbenone(5.72%)
v-f6rh ;na n6 I Rn
o.44 0.66 0.67 0.91 0.62 o.72 2.07 p-crrn9!9(t) geraniol
(1.020/4
p-cymene 0.51 0.73 tt 0.75 0.61 0.87 1.01
t=trace (<0.01%)
camphor 5.80 8.94 6.57 6.35 7.98 9.66 8.30 8.25
linalool 2.OS 2.81 3.00 2.69 0.51 2.60 4.33 4.27 A. Bayrak and A. Akgul, A study on the
bornylacetate 2.76 3.30 7.07 4.43 2. 84 1.90 1.84 1.75 composition of the essential oil tf rosemary.
B-caryophyllene1.06 1.44 1. 74 0. 91 0. 16 1.19 1.17 1. 0 3 Gida Sanyii,r(5),20-22 (1988).
cr-terpineol 0.85 1.09 1. 57 0. 99 1. 47 1.51 2-55 1.75 P. L. Cioni, G. Flamini and I.Morell|Indagine
borneol 4.14 5.00 2.37 2.04 10. 11 B-24 9.09 8.87 preliminare su una coltiaazione di Rosmarinus
verbenone 6.46 6.91 6.80 5.72 6.43 5.94 7.48 5.77
geraniol fficinalis in Prouincia di Pisa: Caralterizzazione
t t 1. 09 1. O 2 0. 92 1.55 1.44 1.13
dell'olio essenziale.RivistaItal. EPPOS, (3), 3-
6 (1991).
M. Jain,R. Banerji, S.K. Nigam, J.J.C.Scheffer
p-cymene(2.8%) (1.9%)
o-terpineol and H. C. Chaturvedi, In aitro production of
(0.2%)
terpinolene borneol(1.8%) essentialoil from proliferatingshootsof Rosmarinusfficinalis.
lenchone(0.37") PlantaMed.,57,122-124 (1991).
P.Kreis,D.Juchelka, C. MotzandA.Mosandl,Chiraleinhaltsstffi
In the analysis on the non-polar column, tricyclene ritherischert)leIX. Stereoclffirenzierungoonborneol,isobonteol
(0. unclbornyI acetate.D eutsch. Apoth.Ztg.,13 1, I I I 4-I I 87( 1991).
' -: and caryophyllene oxide 1 7o) were alsoidentified.
--, in 1993, Chalchat et al. compared the chemical K. P. Svoboda andS.G. Deans,A study of theuariabiliq of rosemary
:-ion of variousrosemary oilsof Moroccan, Spanish and sageand their uolatile oils on the British market; Their
- -:,cfi origins using GC/MS, A summaly of the oils of antioxidantpropefties.FIav.Fragr.J.,7,81-87(1992).
P. SanchezGomez, M. SorianoCano, ]. A. SotomayorSanchezand
E. Correal Castelianos, El Romero en la Region de Murcia, Table Vlll. Comparativechemical composition (%) of
Agricola Vergel (July), 444-449 (1992). Moroccanand French rosemary oils
S. Cataiano,P. L. Cioni, G. Flamini and I. Morelli. Stucliodella,resa
Compound Moroccanoils (7)a Frenchoils (3)a
e dellu composizione chimica di oli essenzialiottenuti cla planta
intera, rami efoglie confiort di Rosmarinus fficl,?zlis. Rivista Ital. tricyclene 0.10-0.23 0.24- 0. 41
EPPOS,(1 0),1 7- 19( 1993) . o-pinene s.56-12.72 19,91- 35. 08
crthujene 0.00-t 0.00-0.08
P. L. Cioni, S. Catalano,G. Flamini and I. Morelli, Indagine su una
camphene 3.21-3.98 5.86-8.35
coltiuozione di Rosmarinus tfficinaLis L. in proaincia dl pisa:
Studio della xariabilita della re,sae della cotnposizione chirLica B-pinene 5.53-7.83 2.08-4.35
d,ell'olio essenziale.Rivista Ital. trppos, (9), 3l-33 (1993). sabinene 0.14-0.21 0.21- 1. 36
6,6-dimethyl[3.
1.1]bicyclo-
Anon, Anahltica,l Methorls Committee, Application of gas-liqticl hepf 3-ene-2-butylene* 0.00-t 0.07-0-78
chronatography to the analqsis of essential oils. Paft XVL 6-3-carene 0.15-0.20 0.1 9- 1. 19
M onographsforfia e es,sential olls. Analyst, I I 8, I 089-1098 (I 993).
myrcene 1.27-1
.60 1.55- 2. 12
J. C. Chalchat,R. P. Garry, A. Michet, B. Benjilali and J. L. Chabart, oterpinene 0.52-0.66 0.39-0.46
Essential oilsof rosem,nry(Ro,smarimtsfficinalis L. ). Thechernical limonene 1.86-2.06 3.02-3.96
composition of oils of oarious origins (Morocco, Spain, France). !. 1,8-cineole 43.53-53.48 5.30-24.79
Essent.Oil Res.,5, 6f3-618 (1993).
(Z)-B-ocimene 0.00-0.27 0.00-0.05
B. M. Lawrence and C.-K. Sht, Essential oils as component,sof y-terpinene 0.93-1.19 0.2 8- 1. 28
mixtures: Analgsis and dffirentiation. In: Flaaor Measurement. (E)-B-ocimene 0.00-0.06 0.02-0.53
Edits., C.-T. Ho and C. H. Manley, pp 267-328,Marcel Dekl<er, p-cymene 0.99-1.40 1.3 9-
1. 54
New York (1993).
terpinolene 0.29-0.36 0.5 1- 0. 78
F. M. Soliman,E. A. El-Kashoury,M. M. Fathy and M. Il. Gonaid, frans-sabinenehydrate 0.04-0.1
I 0.0 9- 0.21
Analysis ancl biological actiaity of the essentialoil of Rosm,arinus viridiflorene 0.00-0.12 0.0 6- 0. 15
fficirtolis L. frorn Egypt. Flav. Fragr. J., 9, 29-33 (1994). camphor 7.42-10.80 3.0 1- 7. 50
S. Perrucci, F. Mancianti, P. L. Cioni, G. Flamini. I. Morelli and G. isopinocamphone 0.04-0.13 0.06-0.58
Nlacchior, In oitro antifungal actiuity of essential oilsagainst some linalool 0,73-1.76 1.4 6- 9. 41
isolateso;fMicro,sponrm canis and Microsponrnt gypseum. Planta linalylacetate 0.00-0.02 0.00-5.52
Med., 60, 184-187(1994). ct-santalene 0.00-0.80 0.00-t
bornylacetate 0.12-0.86 1.19- 14. 32
Laurel Leaf Oil 2.41-4.32
B-caryophyllene 0.0 0- 2.I 1
A sample of laurel leaf oil, which r,vasproduced by steam terpinen-4-ol 0.69-0.91 0.0 0- 1. 21
geranylacetate 0.00-0.07 0.33-0.68
distillation of the dried leavesof Laa rus nobilis of Albanian
origin was analyzedby capillary GC (Borgeset al. 1992).The tI-numutene 0.27-5.43 0.00-0.94
qualitativeand quantitativecompositionof this oil is summa- lavandulylacetate 0.00-0.30 r-0.54
rized as follows: B{arnesene* 0.37-0.51 0.00- 0. 19
lavandulol 0.00-0.23 0.00-0.06
a-thujene(0.3%) terpinen-4-ol (0.9%)
verDenone 0"00-0.46 1.0 3- 5. 08
o,-pinene(2.2o/") o,-terpineol (1.2%)
O,-terpineol 0.00-2.46 0.00-0.09
camphene(0.2%) ner ol( 0. 1% )
sabin en e(1 1.8 % ) borneol 3.00-4.51 3.24-6.53
Iinalylacetate(0.6%) germacrene D 0.00-0.1
3 0.00-t
B-pinene(2.4%) bornylacetate(0.4%)
myrcene(0.2%) eugenol(18.5%) y-muurolene 0.00-0.13 0.00-t
0,-phellandrene (0.2%) a-cubebene(0.2%) B-bisabolene 0.06-0.13 0.00-t
6-3-carene (0.1%) s-copaene(0.1%) cI-caornene 0.08-0.98 0.00-0.08
oterpinene(0.4%) methyleugenol (2.5./.) 6-cadinene 0.18-O.77 0.00-0.07
p-cymene(0.4%) (0.6%)
B-elemene
limonene(0.8%) B-caryophyl lene (1.1o/") nerol 0.00-0.10 0.00-0.05
'1,B-cineole(26.7%)
(E)-methyl isoeugenol (0.1o/o) 3,3,6-trimethyl[2"2.
1]
y-terpinene(0.6%) cr-humulene (0.2%) bicyclohept-1
-en-7-ol- 0.00-0.04
trans-sabinene hydrate(0.4%) eugenylacetate(0.1%) gerantol 0.00-0.05 0.00-t
terpinolene (0.2%) o- s elinene( 0. 1% ) caryophyllene
oxide 0.00-0.10 0.00- 0. 10
linalool(18.5%) B-bisabolene (0.1%)
cis-sabinene hydrate(0.4%) T-cadinol 0.00-0.11 0.00- 0. 12
6-cadinene (0.2%)
borneol(0.2%) thymol 0.00- 0. 18
elem ol( 0. 1% )
carvacrol 0.00- 0. 14
o-bisabolol 0.00-0.27
Also in 1992, Nigam et al. analyzedan oil producedins.\Vo
',ielclfrom the fruits of L. nobilis grown in India using GCIMS. t = trace (<0.01%)
anumberof samples
Trr,:conrpoundsidentifiedwere: *tentativeidentification
*correctisomer
not identified
crthujene(3.81%)
Table lX. Chemicalcompositions (%) of rosemaryoils a-pinene(9.30%)
of differentgeographicorigins sabinene(4.89%)
B-pinene(1.93%)
Compound Spain Morocco Tunisia Yugoslavia Portugal crc-phellandrene(10.07%)
1,8-cineole (28.37%)
o-pinene 19. 1- 35. 8 7.2-7.5 8.6-11.4 15.6-26.5 12.0-25.0 linalool(2.32k)
campnene 7. 0- 10. 0 4.3-4.6 2. 7- 4 . 3 3.2-8.2 1.3-1.9 camphor(2.17o/o)
B-pinene 3.0-7.7 4.9-5.0 2.7-7-7 0.7-2.0 1.5-3.4 terpinen-4-ol (1.39%)
myrcene 1. 1- 6. 0 cr-terpineol(5.85%)
0. 1 1. 1- 1 . 3 1.3-1.9 19.5-52.1
neral(0.61%)
limonene 2.9-5.0 t.z- t.o 1. 9- 4 . 8 2.2-3.3 2.4-10.6 geranial(0.67%)
'1,8-cineole 15. 0- 25. 1 + I. t- +J. I 40. 1- 5 5 . 1 18.5-39.2 4.2-5.6 cl-gurjunene (2.17%)
p-cymene allo-aromadendrene (0.85%)
0.4-2.4 2. 1- 2. 3 1. 1- 1 . 8 1.8-2.0 2.4-6.0
B-caryophyllene (3.33%)
campnor 6.6-20.7 11. 0- 13. 5 6. 4- 1 4 . 8 11.6-14.3 2.1-4.4 methyleugenol(1.16%)
linalool 0.5-2.0 myristicin(1.39%)
0.7-0.9 0. 6- 1 . 3 0.7-1-3 0.4.2.0
6-cadinene (0.07%)
bornylacetate 0.4-4.2 1. 0- 1. 1 o.4-1.2 2.4 0.5-2.0
The followingyear, Pino et al. (1993)
terpinen-4-ol 0.7-2.0 0. 5 0. 6- 1 . 6 0.1 1.8-6.8
compared the chemical composition
B-caryophyllene 1.8-4.3 0. 5 0. 9- 1 . 1 2.9-3.4 t
of laurel leaf oil produced from Alba-
oterpineol/borneol 2.0-5.0 2,9-3.2 2. 8- 1 5 . 9 2.8-6.6 1.3-4.1 nian dried leaf with three commercial
verbenone 0.5-6.0 I r t t-1.8 leaf oils of different geographic ori-
gins. The comparative data found on
t = lrace (<0.1 %)
Table XI describes only the composi-
tion of the three commercial samples
of laurel leaf oil. The composition of
the oil obtained from the Albanian
Table X. Chemicalcomposition (%) of Egyptianrosemaryoil
dried leafis described earlier.
This same year, Biondi et al. (1993)
Gompound Sinai oil Gazaoil Compound Sinai oil Gazaoil analyzed an olIof Laurus nobiliswhich
a-pinene 2.46 9.33 carvone 1.67 0.40 was produced from leaves collected in
camphene 1.63 3.65 cls-myrtanol 1.19 0.27 Sicily. The composition of this oil as
B-pinene 1.20 1. 80 frats-myrtanol 2.32 0.79 determined by GC and GC/MS was
myrcene 0.48 5.39 bornylacetate 7.59 1.98 found to be as follows:

u-phellandrene carvacrol 0.35 0 .1 5 hexanal(0.21%)


0.46 2.24
2-hexenal*(0.23o/o)
s-terpinene 0.27 0.40 sabinylacetate* 0.11
3-hexenol(t)
p-cymene 1.77 6.29 piperitenone 0.27 0.19 lrinrrnlano rrirrna\

1,8-cineole 8.96 neothujol 0.12 0 .1 3 o,-thujene(O.41%)


o-pinene(4.92%)
llmonene t.oa 0{erpinylacetate 0.36 0.16 benzaldehyde (t)
y-terpinene 0.26 0.09 0-copaene 0.14 0.09 camphene(0.81%)
2,5-dimethylstyrenei0.05 0.45 methyleugenol 0.33 0.'18 sabinene(7.11%)
terpinen-4-ylacetate0.89 2.77 B-caryophyllene 2.75 1.54 B-pinene(3.85%)
1-octen-3-ol(0.07o/o)
linalool 6.60 5.44 B-gurjunene 0.05 myrcene(0.65%)
0.93 c-humulene 0.83 0.33 o-phellandrene
B-thujone 0.28
( 0 . 1 5 %)
cls-sabinenehydrate0.03 allo-aromadendrene
0.36 0.10
6-3-carene (0.19%)
camphor 11.29 14. 91 u-muurolene 0.17 crterpinene(0.31%)
p-cymene(0.18%)
trans-pinocarveol 2.25 1. 04 y-cadinene 0.36 0.03
1,8-cineole (34.77%)
c/.s-3-pinanone 1.22 2.BB cis-calamenene 0.13 0.05 limonene(t)
terpinen-4-ol 2.88 z. t3 D-cadinene 0.61 0.22 (Z)-B-ocimene (t)
0-terpineol 4.92 3.27 caryophyllene
oxide 1.31 0.34 (E)-B-ocimene (0.10%)
y-terpinene(0.56%)
verDenone 12.33 7.58 T-muurolol 0.08 B{erpineol*.(0.18%)
borneol 1 .6 9 0.30 epi-o-bisbolol 0.20 terpinolene (0.21%)
linalool(26.89%)
borneol(0.25'/")
.correctisomernot identified terpinen-4-ol (1.35%)
ttentativeidentification o-terpineol (1.33%)
linalylacetate(0.06%)
bornylacetate(0.57%)
acetate(7.35'/.)
cx,-terpinyl Table Xl. Comparative composition (%)
nerylacetate(0.06%) of three commercial laurel leaf oils
methyleugenol(2.02%) of different geographicorigins
B-caryophyllene (0.47%)
B-bergamotene- (0.1B%) Compound Frenchoil Italianoil Spanishoil
y-cadinene(0.07%)
othujene o.4 0.2 0.2
(<0.01%)
t=trace 0-prnene 7.1 15.9 I t.o

P. Borges, j. Pino and tr. Sanchez, Isolation and chemical camphene 2.9 0.9 o .7
choracterizotion of laurel leaf oil. N ahrun g, 36, 494-496 ( 1992). sabinene 4.5 6.5 5 .2
M. C. Nigam, A. Ahmad and L. N. Misra, Laurus nobili,s:An
essential oil of potential aalue. Parfum. Kosmet., 73, 854-859 B-pinene 5.9 6.5 4 .9
(19 92 ). myrcene t.c 0.9 0 .7
a-phellandrene 0.3
J. Pino, P. Borges and E. Roncal, TLrcchemical composition of lourel
leaf oil frorn aarious origins. Nahrung, 37, 592-595 ( 1993). c{,terpinene t 1

D. Biondi, P. Cianci, C. Geraci, G. Ruberto and M. Piattelli,


Antimicrobial actioity and chemical composition of essential oils limonene 0.5 o.2 0. 5
from Sicilian aromatic planfs. FIav. Fragr. ]., 8, 331-337 ( 1993). 1,8-cineole 43.5 38.1 43.0
Y-terprnene 0.4 1.0
hydrate 0" 6
trans-sabinene 0.1 0. 1
Celery Seed Oil
It is ofinterest to note that a number ofyears ago Berger et terpinolene 11
0.2 0. 1
al. (1985) identified 1-(E,Z),3,5-undecatriene(ca. I pglkg linalool o.+ 6.2 6"5
fresh material) as a component of celery root. The occur- borneol 1.1 1.5 0. 1
renceofthis compound in celeryseedoilhasbeenpostulated terpinen-4-ol 2.1 2.2 2. 1
although not unequivocallyconfirmed ( Lawrence).
o-terpineol 1.9 1.7 0. 9
Around this same time, the acids and phenols of celery
nerol I 0.7 0. 7
seedoil were the subjectof study (ter Heide et al. 1986).The
linalylacetate 2.7 0.4 2. 1
authors identified the following constituents in the oil under
bornyl acetate 2-3 o.4
study:
phenol nonanoicacid eugenol 2.5 3.0 1. 2
o-cresol decanoicacid d-terpinylacetate 4.5 7.O 6. 0
m-cresol undecanoic acid methyleugenol 1.4 3.0 3. 8
p-ethylphenol 3-methylbutyric acid
B-elemene 0.2 0.4 0. 2
p-pentylphenol 6-methylheptanoic acid
2,4-dimethylphenol 8-methylnonanoic acid
B-caryophyllene t.5 0.4 0. 1
carvacrol 2-methylbutyric acid
g-humulene 0.2
thymol p-menth-1 -en-9-oicacid
guaiacol p-menth-1(7)-en-9-oicacid eugenylacetate T

4-ethyl-2-methoxyphenol perillicacid 0,-seilnene I I

4-vinyl-2-methoxyphenol benzoicacid
eugenol salicylicacid R-hicahnlana I I t
phthalide
5'-hydroxy-butyl phenylaceticacid 5-cadinene I 0.6 I

butyricacid 2-pentylcyclohexa-2,4- elemol 0. 6


valericacid dienoicacid
t = trace (<0.1%)
hexanoicacid -
6-(1'-oxobutyl)-cyclohex-1
heptanoicacid enoicacid
octanoicacid
linalool(0.10%) c-selinene(1.37"/.)
pentylcyclohexadiene (3.27"/") u-bisabolene(0.12o/")
In 1990,Verghesereviewedthe chemical compositionof
o-terpineol(0.28o/o) 3-butylhexahydrophthalide
celery seed. No new information was presented by this p-methoxyacetophenone(0.48%)(0.12%)
reviewer and the review only covered some of the previously carvone(0.40%) butylphthalide(0.38%)
published data up to 1988.Also in 1990, Halim et al. exam- (E)-anethole (0.61%) sedanolide(17.28%)
ined the chemicalcompositionof freshlydistilled celeryseed
*correct isomer not identified
oil which was produced from seedharvestedln Egpt. The
compounds identified were: The identification of umbellulol, anethole, u-bisabolene
cr-pinene(0.14%) (0.15%)
umbellulol and 3-buryl hexahydrophthaliderequirescorroboration before
B-pinene(1.29%) (1.54%)
B-caryophyllene
(0.13%) they can be acceptedas tme constituents of celery seed oil.
myrcene(3.12'/") cr-humulene
limonene(58.53%) (0.18%)
B-farnesene* In 1992, Choudhary and Koul analyzedthe oil of a se-
(0.10%)
o-phellandrene (8.10%)
B-selinene lected strain of Indian Apium graoeolensby both GC and
t,
I

T GC/MS. They found that the oil contained the following 1-terpinene(20.0%) cuminaldehyde (25.01%)
i
i constituents: terpinen-4-ol (0.3%) p-mentha-1,4-dien-7-al
oterpineol (0.4%) (17.36%)
myrcene(0.3%) cuminaldehyde(21.0o/o) p-mentha-1,3-dien-7-al(5.84%)
limonene(20.2%) p-mentha-1 + p-
,3-dien-7-al e (0.20%\
B-caryophyllen
pentylbenzene(1.0olo) mentha-1 ,4-dien-7-al frans-0,-bergamotene(0.31%)
B-caryophyllene (1.9%) ( 1 e . 0 %)
B-selinene (15.9%) B-caryophyllene (0.3%)
cx-selinene (2.8%) B{arnesene-(0.4%)
butylphthalide(6.3%) carotol(0.6%)
cr-eudesmol + B-eudesmol 'correct isomer not identified
(1.8o/"\
senkyunolidea or isomer The fact that cuminaldehyde was not listed in the compo-
(37.3%) nents identified when the oil was analvzed on a polar column
aalso known as sedanenolideor butyl-4,5-dihydrophthalide r.ras probably a $.pographical oversighr by the jou rnal within
which the original article was found. It would be a strange
Itis unlikelythatthe characterizationofc,-and B-eudesmols
cumin oil if no cuminaldehyde was found as a constituent.
in celery seed oil at levels of L87o is correct. These com-
Also in 1993, Shaath and Azzo analyzed a sample of cumin
pounds are unusual constituentsof umbelliferous seedoils.
seed oil of Eg,ptian origin by a combination of GC/MS and
R. G. Berger,F. Drawert,H. Kollmannsberger andS.Nitz,Natural retention indices on two capillary columns of differing polar-
ocaffrenceof undecaenes j. Food
in somefruits and aegetables.
ity. The compounds identified in the oil were as follows,
Sci.,50, 1655-1656(1985).
cr-ihujene(0.28%)
R.ter Heide,P.J.deValois,D. de RijkeandA.A. Bednarczyk,Acids cr-pinene(0.78'/.\
and Phenolsin SeoenSpiceEssentialOils. Paperpre-sentedat camphene(t)
ACSmeeting,NewYork(April 13-18,1986). sabinene(0.40o/"\
B-pinene(14.640/0)
J.Verghese,
In theKaleidoscope:Celery.
Per{.& Fiav.,f 5(3),55-59 myrcene(0.52%)
(1eeo). o-phellandrene (0.63%)
p-cymene(4.91"/")
A. F. Halim, M. M. Mashaly,O. Salama,A. F. Ali and P. Sandra,
B-phellandrene (0.30%)
Analysis of celery fruit oil and inaestigation on the ffict of
limonene(0.37%)
storage.Egfpt. I. Pharm. Sci.,31, 107-113(1990).
y-terpinene(19.12%)
D. K. Choudhary and B. L. Kaul, Volatile aroma constituents of t=trace (<0.01%)

celery (Apium graoeolens L. oar. dulce a: RRL-85-1). Indian


Perfum.,36(1), 17-19(1992). This sameyear Borges and Pino (1993) used a combina-
B. M. Lawrence, unpublished information. tion of column chromatography, GC (for quantitative data)
and GC/MS (for component identification) to examine the
compositionof a lab-dlstilled cumin oil which was produced
CuminOil
from ground dried fruit (seeds)of Turkish origin. The com-
In 1981,Takahashiet al. reported that cumin oil contained pounds that were identified were:
n-iintsulfide asa trace constituent. Twelve yearslater (Anon
o-pinene(1.2%) bornylacetate(0.2%)
1993),a sampleof Eg'ptian cumin oil, which was analyzed
B-pinene ( 1 9 . 9 %) B-caryophyllene (0.1%)
both by GC/MS and by Kovats indices on two capillary myrcene(1.5%) terpinen-4-ol(t)
columns of differing polarity, was found to contain: o-phellandrene (0.2%) methylchavicol(i)
1,8-cineole (0.4%) a-terpineol(t)
o-pinene+ othujene (1.2%) terpinolene(0.1%)
limonene(0.3%) cuminaldehyde (18.7%)
B-pinene(21.O%) terpinen-4-ol(0.5olo)
yterpinene (29.1o/") perillaldehyde (2.4%)
myrcen e(1 .1% ) B-caryophyllene (0.3%)
p-cymene(25.2%) benzylcinnamate(t)
o-phellandrene (1.4%) o-terpineol(0.3%)
linalool(t)
cxterpinene (0.1%) p-mentha-1,3-dien-7-al(11.0%)
t=trace (<0.1%)
limonene(0.7%) p-mentha-1,4-dien-7-al(8.9%)
B-phellandrene + 1,8-cineole carotol(0.5%)
(0.5%) cuminalcohol(0"2%)
K. Takahashi, S. Murah and T. Yoshida, Sqnthesisand distribution
y-terpinene(20.0'/.)
of (-lmint sulphide, a noael sulfur-containing sesquitelene.
p-cymene(9.7%)
Agric. Biol. Chem.,45, 129-131(198f).
Lnon, Analytical Methods Committee, Application of gas-liquid
Analysisof this sameoil on a non-polar column revealed chromntography to the analysis of essential oils. Paft Fy'I.
the following composition: Monographs for fiae e,s,sentialolls. Analyst, 118, f089-1098
( 0. 11% )
t er pinolene
(1ee3).
athujene (0.4%)
o,-pin en(1
e .1% ) terpinen-4-ol (0.16%) N. A. Shaath and N. R. Azzo, Es,sentialoils of Egypt. In: Food
p-menth-3-en-7-al (3.83%) Flaa ors, In gredi ent s and Comp o sition. Edit., G. Charalambous,
B-pinene(21.0%)
p-cymene(9.4%) crterpineol(0.05%) pp 591-603,Elsevier Sci. Publ. BV, Amsterdam (1993).
Davana Oil
In 1979, Takahashiet al. reported that a trace amount of R O.l | _

mint sulfide had been chaiacterized as a constituent of


davanaoil. Two years later, these sarneauthors (Takahashi \;/"\o
et al. 1981)reported that an Indian oil of davanalr'asfound 2a R =H
b R =OH
to containgermacreneD (0.17%) and mint sul{ide(0.0i 67o).
It is worth noting that of the 77 different essential oils ll
screened,davanahad the highest mint sulfide level.
A number ofyears later Catalan et al. (f990) extracted 'YY;Ao\o
the aerial parts of dried Atten'tisia pallens Wall. that was
3ac O H
gror,r,nin the Periakulam region of Madurai district in Tamil b p-oH
\adu (India), and subjecteclthis extract to :rnalysisusing a
lt
combination of modern analr,ticaltechniques.After initial t'qfi o\\
column chromatographyof tle extract over silica gel using
ethvl acetateas the ehiant, a number of subfractionswere Fi gure1.
5a,b
1, davanone;
corrbined and processedby HPLC to yield a number of 2a. 2-hydroxy-isodavanone;
sesquiterpeneketonesthat were characterizedby MS. IR, 2b. 2-hydroperoxy-isodavanone;
:H-\\IIR and 13C-NMR(seeFigure 1). 3a. cis3-hydroxy-allo-davanone;
3b. trans3-hydroxy-allo-davanone;
In 1991, Misra et al. used a combination of column 4. 3,4-epoxy -2-hydroxy-isodavanone ;
rlroniatography,TLC, GC, GCiMS,IR, rH- and 13C-NMR 5a. c/s-3,4-epoxy-allo-davanone;and
:r perforrn a detailed analysisof davana oil which they 5b. f,,ans3,4-epoxy-allo-davanone.

r::',,clucedin the lab by hydrodlstlllation of dried plant


rr.:ierjal. The compounds identified in this study were:
dihydrorosef urans (2.0olo)
:amphene(t) davanaether(1.5%) oxo-nerolidol(2.0%) davanafurans(1.0%)
>acinene(t) davanol(0.8%) artemone(1.7%) davanaesters(0.7%)
i-cymene(0.8%) trans-davanaluran (1.0%) davanaethers(1.5%) hydroxydihydrorosef uran
-alool(0.5ol.) cls-davanaf uran (0.5%) (0.5%)
2 :r-t3-methylbut-2-enyl)-4- artemone(1.5%) On reading the paper of Kak, it was di{Ticult to determine
methyl-2,5-dihydrofuran a nor-diterpenoid furan.(2.0%) horv the author obtained this analysis. The best guess is that
t.l.5"k) hydroxydihydrorose furan he summarized some of the previously published literature
2 3-{3-methylbu t-z-enyl)- - (0.5%)
rnethyl-2,5-dihydrof
uran although he did not cite all of it.
y-cadinene (0.8%)
\1.0% ) farnesol-(0.5%)
rorneol(0.5%) a sesquiterpene alcoholfuran* K. Takahashi,S. Muraki, T. Yoshida,C. Kabuto, T. Ohnuma and T.
-or-davanone (1.5%) ( 1. 5% ) Kato, Minute cotLponent,sof peppernint oil2. Synthesisof u neu
,acaldehyde-(0.5%) trans-hydroxy-davanone(2.0%) sulphur corLtaining cotnpound ntint sulphide anrl its distribution.
ethyldavanate(0.7%) cls-hydroxy-davanone (3.0%) Koen Yoshishu Koryo Terupen oyobi Seiy-uKagaku ni kansuru
;nalooloxide-(0.5%) B-oxonerolidol (0.5%) Toronkai, 23rd, 36-38 (1979).
isodavanone (3.0%) cinnamylcinnamate(2.0%)
lrans-davanone(5.0%) 11-hydroxy-8-oxo-9,1 0- T. Takahashi, S. Nluraki and T. Yoshida, Stlnthesisand clistribution
cls-davanone(38.0%) dehy dr o- 10,1-1 of (-)-rnirtt atlphide, a nouel sulplrur-containing sesquiteryene.
nor-davanaether (t) dihydronerol idol(2.0%) Agric. Biol. Chern.,45, 129-131(1981).
nerol(1 0.0 % ) davanicacid (2.5o/.)
geraniol(5.0%)
C.A.N. Catalan, M. Del R. Cuenca, J. Verghese,M. T. joy, A. B.
lilacalcohol.(0.5%)
Gutierrez andW . Herz,Sesquit eryteneketonesrelatedto datanone
- correct isomer not identified
from Artemisia pallens.Phltochenistry . 29.2702-2703 (1990).
l=trace (<0. 1%)
L. N. Misra, A. Chandra and R. S. Thakur, Fragrrmt corrrytonentso.f
\Iore recently,Kak summarizedthecompositionofdavana oilfron Ar-ternisiapallens.Phltochemistry, 30, 549-552(I991).
oiI as follorvs:
davanones (52.O%) geraniol(8.0%) S. N. Kak, Dra:ana oil-An essentialoil of great bnf)oftance to per-
n er ol( 11. 0%) (3.5%)
hydroxydavanones .fumery irrchtstnl.Parfum. Kosrnet.,74(2),i6-7 r-(1993).
Progress in Essential Oils
Reprinted
fromPerfumer
& Flavorist, 1995,Vor.20, No.2, p.49
March/April

PepperOil and Extract formylpiperidide


acetylpiperidide
In 1981,Takahashiet al. reported that Indian blackpepper oil
dodecanoylpiperidide
contained germacreneD (0.92Vo)and mint sulfide (0.002Ea) hexadecanoylpiperididet
as minor comDonents. 9-octadecenoylpiperididet
A number of years later, Pino et al. (1990) used Kovats (2E)-decenoylpiperidide
Indices on a polar capillaryGC column and GC/M S to analyze (2E)-dodecenoylpiperidide
(2E){etradecenoylpiperidide
a lab-prepared sample of black pepper oil produced from
(2E)-hexadecenoylpiperidide
Indian peppercorns.The compoundsidentified in this analy- (2E,4E)-decadienoylpiperidide
siswere: (2E,4E)-dodecadienoylpiperidide
3-phenyl-(2E)-propenoylpiperidide
cr-thujene(0.8%) 6-elemene(t) 3 (3,4-methylenedioxyphenyl)-2-propenoylpiperidide
o-pinene(8.2%) (t)
B-elemene 5 (3,4-methylenedioxyphenyl)-2-pentenoylpiperidide
(piperanine)
cam p he ne(0.1 % ) o-copaene(0.2%) 7 (3,4-methylenedioxyphenyl)-6-heptenoylpiperidide
(piperolein
A)
sabin en e(1 9.0 % ) (10.0%)
B-caryophyllene 9 (3,4-methylenedioxyphenyl)-8-nonenoylpiperidide
(piperotein
B)
B-pinene(12.o%) a-humulene(0.3%) 5 (3,4-methylenedioxyphenyl)-2,4-pentadienoytpiperidide-
myrcene(1.2%) o-guaiene(t)
o-ph ella nd ren(1.3
e %) ry-nr rhahana /t\

6-3-carene (16.0%) ar-curcumene (t) Table l. Comparativepercentagecomposition


o-terpinene (0.1%) 6-9uaiene(t) of the monoterpene hydrocarbons of
p-cymene(0.3%) o-selinene(0.6%) Muntok pepper oil and CO, extract
(Z)-B-ocimene (0.1%) 1F\-R-fa rnacana /+\
lim o ne ne(1 9.0 % ) (0.6%)
B-bisabolene Compound
(E)-B-ocimene (0.1%) 6-cadinene(t) oi l Extract
y-terpinene (0.2%) p-selinene
(t) tricyclene 1 I
terpinolene (0.2%)
cx,-thujene 0.17 0.22
t=trace (<0.1%)
o-pinene 9.65 9 .4 8
Two years later, Kollmannsbergeret al. (1992) compared crjenchene 0.04 0.04
the chemicalcompositionofthe volatilepoftion of a supercritical camphene 0.32 0.33
CO, extract of Muntok pepper with that of an essentialoil
sabinene 0.21 0 .2 2
produced from the samebatch ofpepper. The resultsofthese
p-pinene 15.81 15.22
analysescan be seenin Table I. In addition, trace amountsof
myrcene 3.62 3.72
a fervother compclnentsr,verealso{bund in the extractbut not 6-2-carene o.02 0.02
in tlie oil. These minor corrDonenrswere: CI-phellandrene 4.93 5.24
perillene mynenol 6-3-carene 35" 91 35.84
cls-p-menth-2-en-1
-ol isopiperitenol- o,terpinene 0.20 0 .2 1
sjenchol trans-carveol m-cymene 0.17 0 .1 6
borneol cls-carveol p-cymene 2.31 2 .1 4
c-caranonet limonen-10-ol
myrtenal limonene 24.25 24.66
carvacrol
B-phellandrene 0.52 0 .6 1
- correct isomer not given (Z)-B-ocimene t 1
(E)-B-ocimene 0.01 0. 01
In this same report, a comparison between the sesqui- a p-menthadiene* 0.05 0. 07
,eryene hydrocarbons, oxvgenatedmonoterpenes,oxygen- yterpinene 0.23 0.24
:ted sesquiterperesand miscellaneouscompoundsin the oil cx,-m-dimethylstyrene t t
-.nd extract can be seenin TablesII-V respectively. a p-menthadiene. 0.39 0.42
Also in 1992, Kollmannsbergerand Nitz used a combina- terpinolene 0.93 1. 00
ron of GC/MS and GC/FTIR to analyzethe amide composi- tI-p-dimethylstyrene 0.04 0.04
ron of a supercritical CO, extract of Muntok pepper. The p-mentha-1,3,8{riene t t
'rmpoundsidentified were as follows: a p-menthatriene* t t
t = trace(<0.01%)
'correct i somernot gi ven
(0.00-002%) caryoPhYlleneoxide
p-menth-B-en-2-ol
(0.25-0.e0%)
5 (3,4-meihylenedioxyphenyl)-2'4-pentadienoylpiperidide* trans-caNeol (0.00-0'02%)
cedrol(0.00-0.05%)
s ii,+-t"il'tVr.nedioxyprrenyt)-(2E'4E)-pentadienoylpiperidide cls-carveol+ carvone
(piperine) ( 0 . 0 1 - 0 . 0 3 %) a cadinol"(0.12-1
-51%)
z tii-."t'vr"nedioxvphenvr) a cadinol*(0.12-0'26%)
?,?Ppt"9l:l"1!lf:'^oio"' piperitone(t-0.04%)
(0.09-020%)
7 (3,4-methyleneoioxypnenytj-2'4'6-heptatrienoylpiperidide carvoneoxide"(0.00-0'01 %) B-bisabolol
(ZL.+e)-OecaOienoylpyrrolidide myrtenol(0.04-0.11%)
izf ,+e)-OoO""adienoylpyrrolidide o-terpinYlacetate
i1e,+-mettrytenedioxvphentll)-? Ptt*""vllv:::llll:: (0.86'1.33%)
i i g.+-."t|'vr"nedioxyphenyl)-6-heptenoylpyrrolr0roe
s is.+-mettrytenedioxvphenvl)-B-nonenovlpvrr"l::i:,"^,,. * correci isomer not glven
s ii.+_."tnvr"nedioxyphenyl)_2,4-pentadienoylpyrrolidide l=trace(<0.01%)
(piperyline) ol clovene'
The authors indicated that their identification
7(3,4-methylenedioxypnenyl)-2'6-heptadienoylpyrrolidide 6-guaiene'
fzL.+f)-decaOienoyl-isobutylamide g"rt;;;;;. D, B-bisabolene' cr-bisabolene'
izE,+ri-ooo".adienoyl-isobutylamide
rzE.+Ei-f,e*aOecadienoyl-isobutylamide
ize.+E)-octadecadienoyl-isobutylamide Table
'"- ll. Comparative percentage compos-ition
2,4,9-octadecatrienoyl-isobutvlamide of tn" sesquiterpenehydro^carbgn:-in
5 (3,4-methylenedioxvpnenvl j-2-pentenovl-isol1t1]ii'd" niiuntof.p'"pperoil and CO, extract
; );.;;;ili,i;n"Jio*vbr'"nvri-2'4-pentadienovr-isobutvramide
oil Extract
i tentative identification Compound
- correct isomer
- - - - r : ^^- ^" not given
- ^+ ^iv 9.1 9. 6
6-elemene
any detailed quanti- 0.4 0. 3
Although the authors dicl not present cr-cubebene
3. 2
that the major components 4.4
tative infbnliation, they dicl state c[-copaene t
(567o)'piperolein A (l2Ea)' (Z)-P-elemenei
I
of the CO, extract$/erepiperine r' 0.6 o. 4
r9 7 o pi pel etti ne p-cubebene
Bo ' o' ' p i p e rv l i n e
e 7.p i p e ro l e i n ' tl
n i oc r anir r16% (37o
dleno'lpiperidide) 1.4 1. 5
iif iJ,ilil'jlii"Jt"","pl'"".vth"pt"
(27o)'
(E)-B-elemene
0.1 0. 1
ancltr,voisomei'sof piperine of
CI-gurJunene
-'l; composition
,;il, a"p"1"l-tih;;" "i ol"""uly'eclthe
t
isocarYoPhYllene o. 2
ol P i per o.2
..ilq nr or luc ed l ro m { o u r s e l e c te d c u l ti v a rs a guaiene*
75.2 73. 5
;;;];; ;;;i of ctipillaw GC.(KovatsIndices) B-caryoPhYllene
""*r'*"t'ncharacterizedthe follor'vingconstitu- I I
anclGC/lvlS the authors y-elemene
t
ents: frans-0,-bergamotene
t 0. 1
nervlacetate(0.05-020%) ([-gualene
3.7
o,thujene(0'73-159%) oeranvlacetate(0.01-0'12%) o(-humulene
3.4
(5.07-61B%) t t
cr-pinene Ir-cunlbene+ 8-elemene(0 16- y-guaiene
ca mph en e(0.1 3- 0. 18% ) 3.25%\ 0. 2
0.1
sab ine ne(1 '94 -17' 16% ) cr-copaene(0.44-O'82%) (E)-B-farnesene
I
p-pinene(6.40-1 1.08%) (0.05-0'09%)
I
B-elemene Y-gurJunene 0 .1
mvrcene(220-8.40%) 0.'1
p-caryoPhYllene Y-muurolene
6r-phellandrene (0'00-2'32%) 0.2 0 .4
(21.19-23.29'/") germacreneD
6-3-carene(0.0O-282"/') 0.7 0 .6
frans-cx-bergamotene p-selinene
o(terPinene (0.00-0'39%)
(0.00-0.28%) T I
p-cymene(0.00-970%) (0.11-0 29%) ar-curcumene
cr-humulene 0.6
iz;-P-ocimene + B-Phellandrene (0 03-022"') g-selinene
(E)-ll{arnesene T
(0.00-0.37%) (1 28-154") t
a-amorPhene bicyclogermacrene o- 4
limonene(16'74-22'71"/") cr-guaiene (0.00-011%) germacrene A I
(E)-B'ocimene (o.17-2'84%) t t
clovene (0.07-0.14%) 6-guaiene
y-terPinene(0 00-0 49%) qermacrene D (0'03-0'26%) 0. 2
irans-sabinenehYdrate
0.2
lu.rt.ut"n" (0.04-0'29%) B-bisabolene I
I
(0.00-0.30%) (0 63-1'37%) (E,E)-a{arnesene
(0.08-0'22%) P-selinene t.J 4-2
terpinolene a-selinene(0.07-048%) germacrene C
oxideJuranoid t t
frans-linalool v-muurolene (0.16-0'93%) calamenene
(0.00-0.18%) (0 00-072%) 1.5 1 .1
iE,E;-oJutn"t"ne 6-cadinene
linalool(0 22-0.46%) + o(-bisabolene 1
1-ol + cls-P- B-bisabolene t
cis-p-menth-2-en- (0.49-4.25%) p-sesquiPhellandrene
-ol (0'02- I t
mentha-2'B-dien-1 (0.09-185%) cadina-1,4-diene
E-guaiene t t
0.05%) cuparene (0.04-1'38%) a calacorenet"
irans-p-menth-2-en-1 -ol (0'01%) 3%) I I
b-cadinene (0.00-0'1 germacrene B
(0 01-0.03%)
citronellal (0 05-0 20%) t t
(Z)-nerolidol cadalenel
p-menth-8-en-1'ol (0 00-003%)
elem ol( 0. 06- 0 . 1 1 %)
borneol(t) (E)-nerolidol (0.03-0' 12%) I tentativeidentification
terpinen-4-ol (0.18-0'52%) * correclisomernot given
caryoPhyllene alcohol
cr{erPineol(0'07-017%) t = trace(<0.1%)
(0.02-0.07%)
drhYdrocarveol (0 00-0 02%)

l0

I
cuparene, cedrol and the tr,vocadinols was tentative requiring identified
in the extract, they did characterize the following
independent corroboration before being fully acceptedas a compounds:
black pepper oil constituent. citronellal
a-pinene
Also in 1993,Hossainet al. comparedthe major volatilesof B-pinene B-caryophyllene
white pepper before and after the spice had been irradiated myrcene carvone
with y-rays. Although the authors found that the volatiles in limonene methyleugenol
p-cymene eugenol
white pepper did not show any significant changes,standard
volatile oils showedthat irradiation causeda marked decrease
K. Takahashi,S. Murah and T. Yoshida, Synthesisand distributiort, of
in 6-3-careneand limonene contents while the levels of cr-
(-)-mintsulphide, a noael sulfur-containing sesquiterpene. Agic.
pinene, myrcene and B-caryophyllenereportedly increased. Biol. Chem.,45, 129-131(1981).
As no statistical evaluation of this study was performed, the
results presented are suspectand require corroboration be-
fore thev can be accented.
More recently, Yasumoto et al. (1994) reported that the Table lV. Percentagecomposition of oxygenated
black pepper could be efficiently extractedusing liquid CO, sesquiterpenesin Muntok pepper oil and extract
at pressuresof 70-200 kg/cc at 20'C. When they introduced
ethanol (0.5-2.0Ea)into the extractingsolvent,the extraction Compound oi l Extract
efficiency towards piperine was increased.Although the au- isocaryophyllene
oxide I I

thors did not present any quantitative data on the volatiles caryophylleneoxide 0.2 0. 9
cr-humulene-1,2-epoxide I I

Table lll. Percentagecomposition of (E)-nerolidol I

oxygenatedmonoterpenoidcompounds in spathulenol t
Muntok pepper oil and extract T-muurolol I

o-bisabolol I
Compound oil Extract
s-cadrnol I
1,8-cineole 0 .2 0.4
selin-11-en-4-oll I t
lrans-sabinenehydrate I I
cadina-5,10(15)-dien-4-olt 0.2 1. 3
fenchone I I
cls-sabinenehydrate I I B-humulen-1-ol t
linalool 0 .8 u.b caryophyllen-5-ol
I t
caryophyllen-5-ol
ll I t
a p-menthadienol- I I
caryophyllen-5-ol
lll i
lrans-p-mentha-2,8-dien-
1-ol I I
caryophyllen-5-ol
lV I
c/s-p-mentha-2,8-dien-
1-ol I I
4-5-epoxycarene I I i tentativeidentification
a-pineneepoxide I I t = trace(<0.1%)

frans-pinocarveol I I
campnor I I
trans-p-menthan-8-ol I I Table V. Percentage composition of some
prnocarvone I I miscellaneouscompounds in
m-mentha-1,3-dien-8-olt 0.2 0.2 Muntok pepper oil and extract
p-mentha-1,5-dien-B-ol I I
3-pinanone* I I Compound oi l Extract
terpinen-4-ol 0 .3 0.1 methylpiperinate t 0. 2
oterpineol 0.2 0.2 methylcitronellate 1 t
B-phellandren-6-ol 0 .1 0.2 linalylacetate t
a phellandrenol.t I I a terpinylacetatet t
1,4,4-trimethylcycloheptadienone- I I cxterpinylacetate 1
crs-piperitol T I
2-undecanone t t
l terpinen-5-ol I T
hanzaldahrrdo t t
a phellandrenol-i I t
p-cresol I t
carvone o .2 1 m-cresol t t
2-caren-3-onet I I
p-methylacetophenone t t
piperitone I I
3,4-methylenedioxystyrene t
3-caren-2-onei I 0.2
3,4-methylenedioxybenzaldehyde 0.1 0. 5
carvacrol t I
3,4-methylenedioxycinnamaldehyde 0. 2
* correctisomernot identified
t tentativeidentification I tentativeidentification
t = trace (<0.1%) t=trace(<0.1%)

11
J. Pino, G. Rodriguez-Feo,P. Borgesand A. Rosado,Chemicaland of GC and GC/MS in the El mode and C.I. mode, the oils and
sensory propefties of black pepper oil. Nahrung, 6, 555-560 extracts were analyzed, the results of u'hich can be seen in
(199 0).
Table VII. It is of interest to note that CHr-Cl, extract of the
H. Kollma nn sb erg er , S. Nit z and F. Dr awer t , U b e r d i e plants produced from the Vietnamese seed was richest in
Aromastoffzusamtnensetzungaon H ochdruckertrnkten LPfffir
(P\ternigrumaar. Muntok).Zeit. Lebensmitt. Untersuch. Forsch., arteannuin B, the antimalarial constituent of A. annua.
194, 545-55r (1992). In 1994, Chalchat et al. compared the composition of
French and YugoslavianA. annuo oil produced from plants
M. Gopalakrishnan,N. Menon, K. P. Padmakumari,A. jayalekshmy
harvested at different maturity stages.A summary of their
and C. S. Narayanan, GC analysis and odor profiles of four new
Indiangenotypesof PipernigtumL. j. Essent.Oil Res.,5,247-253 results can be found in Table VIII. The authors found that
( 1993). although the o,-pinene and artemisia ketone contents were
fairly similar in oils produced when the plants were haruested
H. Kollmannsberger and S. Nitz, Saureamidein Hochdntckertrakten
in the budding stages,the artemisiaketone content reacheda
aus Muntok-Pfffir. Chem. Mikrobiol. Technol. Lebensmitt., 14,
87-94(1se2). ma.ximumin plants that were hawested towards the end of the
flowering period. In addition, the oil content of plants in the
S. N. Hossain, Y. Watanabe and I. Ishigaki, Chemical changes in
budding stagewas 0.02-0.09Vowhile plants at full flowering
Jlat:oring com,ponentsin white pepper (Piper nigrum L.) due to
galmna irradiation. Bangladeshj. Sci. Res.,28(3), 76-84 (f 993). possessed an oil content of 0.15-0.437o.
D. j. Charles, j. E.Simon,Chmonerkationoftheessen-tialc,il
E.Cebeftand
M. Yasumoto, T. Okazaki, T. InaLrrma and T. Kobayashi, Extraction
oJ.Artemisiaannua L. l. Essent.Oi1 Res.,3, 33-39 (1991).
of pipe4ne and aolatile compoundsfromblack pepper u'ith liquid
carbon dioxide. Nippon Shokuhin Kogro Gakkaishi,4l, 102-107
(1ee4). Table Vl. Comparative chemaical composition of the
feaf and flower oil of Artemisia annua

Artemisia annua Oil Compound Leaf oili Flower oil


In 1991,Charleset al. comparedthe chemicalcompositionof
santolinatriene 0.04-0,20 0. 16
the leaf oil and flower oil of Artemisia annua ralsedin Indiana. crthujene 0.01-0.10 0. 13
Using GC/MS astheir method of analysis,the authorscharac- c[-prnene 0.40-0.50 0.24
terized 32 constituents(Table VI). sabinene 1.10-3.80 2.60
This sameyear,Chalchatet al. (199f ) examinedan oil ofA. B-pinene 0.80-1.40 1. 20
annua producedin Yugoslaviausing a combination of GC and (E)-6-methyl-3,5-heptadien-2-one
0.71-0.94
CC,/\IS. The compoundsidentifiedin this oilwere asfollows: d-terpinene 0.22-0.40
2-methylpentan-2-ol (0.60%) isopinocamphone (0.03%)
1,8-cineole 8.70-28.1
0 ).ro
acetone(0.03%) pinocarvone(0.06%) artemisiaketone 26.85-35.60 56.00
1-penten-4-ol (t) bornylacetate(O.21o/o) camphenehydrate 0.14-2.31 2 .0 9
santolinatriene (0.03%) lrans-pinocarveol (0.27%) artemisiaalcohol 0 . 7 2 - 1. 9 0 2 .1 0
lricyclene(0.08%) menlhol(0.43"/.) crs-sabinenehydrate 0.28-0.33
c-pinene (1.26%) 3-thujen-2-ola. (t)
ethyl2-methylbutyrate (0.30%) p-menth-3-en-8-yl acetate sabinol. 0.00-1.70 0.72
camphene(1.48%) ( 0. 11o/ o) camphor 0.00-20.48 10. 50
B-pinene(0.18%) verbenone(1.56%) sabinaketone 0.14-0.55 0.23
butyl3-methylbutyrate (0.30%) borneol(0.18%)
terpinen-4-ol .84
0.14-1 1. 10
p-phellandrene (t) carvone(0.30%) myrtenal 0.20-0.50 0.40
(11 .66 % )
1.8 -cin eo le 3,3-dimethylcyclohexyl idenyl- uterpineol 0.08-0.12 0.09
p-mentha-3,8-diene (0.04%) acetaldehydei(0.05%) myrtenol 0.10 0. 14
p-cymene(0.90%) cuminaldehyde (0.16%) p-ethylcamene 0.04-0.33 0.02
pinocamphone(0.29%) trans-carveol (0.20"/")
artemisiaketone(52.50%) p-cymen-8-ol (0.19%) isoeugenol* 0.04-0.11 0.03
artemisiaacetate(0.12o/o) benzylisovalerate(0.21%) longipinene 0.15 0. 10
artemisiaalcohol(2.07%) caryophyllene oxide(1.91%) benzyl3-methylbutyrate 0.90-0.36 0. 61
menthone(0.23'/.) T-cadinol(t) c)(,-copaene 1.10-1.55 0. 31
frans-sabinene hydrate(0.06%) arteaminine B (0.11%)
B-cubebene 1.80-4.43 0.94
a-ylangene(0.09%) methylchamazulene*(0.22o/o)
B-caryophyllene 5.00-5.60 3.30
camphor(10.90%) artemicitene(0.29%\
' tentative identitication
cr-humulene 0.03-0.71 0. 01
a also known as umbellulol B{arnesene* 0.84-3.80 2.60
' correcl isomer not given
t = trace (<0.01%) Y-eremene 0.40-0.66 0. 11
B-cadinene 0.18-0.50 0.37
T\r'o r-earslater, Woerdenbag et al. (1993) compared the allo-aromadendrene 2.02-8.45 0.06
chemical composition of the essentialoils and methylene caryophylleneoxide 0.95-1.75 3.26
chloride extracts of A. annuo grown in the Netherlands from * correctisomernot identified
t combinationof analysisof same planting2 seasonsin a row
seedof Chineseand Vietnameseorigin. Using a combination

t2
j. C. Chalchat,R. P. Garry,A. Michet, M. Gorunovicand D. Stosic,
TableVlll.Comparativechemicalcomposition(%)of
A contribution to chemotaronomll of Artemisia anrrua L.,
Artemisiaannuaof Frenchand Yugoslavianorigin
Asteraceae.Acta Pharm. Jugoslav.,41, 233-236 (1991).
harvestedthroughouttheir growthcycle
H. J. Woerdenbag,R. Bos, M. C. Salomons,H. Hendriks, N. Pras Compound Frenchoil Yugoslavian oil
and T. M. M alingr6, Volatile constituent s of Art emisia annua L.
(Asteroceae).Flav. Fragr. I., 8, 131-137(1993). tricyclene 0.01-0.35 0. 10
0-pinene 4.20-15.66 1. 25- 7. 00
j. C. Chalchat, R. P. Garry and J. Lamy, InJluence of harcest time a-thujene 0.00-0.90
on qield and composition of Aftemisia annua oil produced in bornylene 0.00-0.29
France.J. trssent.Oil Res.,6,261-268(1994). ethyl2-methylbutyrate 0.00-0.17 0.20-0.30
campnene 1.20-7.28 1, 50- 2. 45
TableVll.Comparative chemicalcomposition(%) p-pinene 0.93-3.35 0.20-1.10
of Artemisiaannuaoils and extracts sabinene 0.43-2.80
3-methylbicyclo-[3.1.2]-oct-2-enei
0.00-t
of differentseedorigins butylisovalerate 0.00-0.14
o,-phellandrene 0.00-t
Chinese seed Vietnamese seed myrcene 0.00-3.34
Compound oil CH2C|2 oil C H 2C | 2 cx-teroinene 0.00-0.18 0.00-0.14
exlract extract 2-oxa-bicyclo-[2.2.2]-oct-6-enet
0.00-0.1
5
limonene 0.09-0.57
artemisiatriene 0 .1 1,8-cineole 5.07-14.68 7 .5 0 - 1 1 .6 5
0,-thujene I I y-terpinene 0.07-0.34
cr-prnene o.4 0 .5 (E)-B-ocimene 0.00-0.27
campnene 1.0 2 .3
p-cymene 1-1.23 0.25-0.90
sabinene I I
terpinolene 0.00-0.33
B-pinene 0. 1 0.2 0. 1 0.4 artemisiaketone 11.91-55.02 37. 10- 52. 50
myrcene 3. I 2 .1 0.9 0.4 isovalerate 0.00-0.31
3-methyl-3-butenyl
yomogialcohol no 0 .4
santolinaalcohol t-0.22
yomogialcohol 0.06-0.64
p-cymene 0 .7 0.4
isopinocamphone 0 .1 I artemisiaacetate 0.00-0.07 0.15
frans-sabinenehydrate 0.00-0.43 0.05-0.45
'1,8-cineole I o-campholenic aldehyde 0.00-0.66
(E)-2,7-dimethylocta- cr-copaene 0.00-1.33 0. 10- 12. 30
camphor '|.58-11.52 1.70-10.90
4,6-dien-2-ol 0 .3
ademisiaketone 63.9 artemisiaalcohol 0.00-11.95 1 . 10-.170
y-terpinene (Z)-3-hexenylbutyrate 0.00-r
lrans-sabinenehydrate pinocamphone 0.00-0.32 0.05
B-cubebene o.09-2.17
artemisiaalcohol 7.5 5 .3 cls-sabinenehydrate 0.11-0.83
cls-sabinenehydrate 0 .5 0 .2 tt prnocarvone 0.24-2.19 0 . 05-.110
camphor 3 .3 4 .9 2 1.8 15.3 B-caryophyllene 1.63-10.87
cls-chrysanthenol 0 .3 0 .2 0 .5 t terpinen-4-ol 0.13-0.38
borneol 0 .2 0 .2 1 .3 0.2 myrtenal 1-0.42
3{hujen-2-ol"- 0.00-2.16
terpinen-4-ol 0 .5 frans-pinocarveol 0.35-1.81 l.oo-z.ts
cr{erpineol 0 .1 cr-himachalene t-0.97
p-myrcenehydroperoxide o-humulene 0.00-0.74
c(-myrcenehydroperoxide (Z)-B{arnesene 0.00-1 .10
bornylacetate o .t (E)-B{arnesene 0.00-1.00
rlerylacetate o .4 DOrneol 0.00-0.16 o.zo
aterpineol 0.00-0.65
trans-chrysanthenylacetate - 0 .3 0.2 germacreneD 1.99-18.54
cis-chrysanthenylacetate 0 .3 0.2 cI-guaiene 2.24-14.73
c{-copaene 0 .7 1.5
bicyclogermacrene 0.16-1.28
3-elemene 0 .2 0.1
frans-(3,3-di
methyl)cyclo-
3-caryophyllene 2 .5 0"5 c.o J, I hexylideneacetaldehydet 0.00-0.41
c{-numulene t 0 .3 o-cadinene 0.00-1.05
6,6-dimethyl[3.
1.1]-bicyclohept-
, E)-p{arnesene 1. 3 0 .3 3 .8 1.2
2-en-2-methanolr 0"08-0.67
germacreneD 1 8 .3 0.8
4. 7 0 .6 0.3 isocaryophyllene
oxide 0.04-0"39
caryophylleneoxide 0.10-1.64 0 . 10- 1. 90
-,€lemene t.J spathulenol 0.00-0.49
a cadinenol* 1a
0"3 nootkatone 0.00-0.82
a'leannuicacid t 1.8 cedrol 0.00-t
a'.ieannuinB o.z 14.9 thymol 0.00-0.83
a'iemisinin 1. 7 22.3 carvacrol 0.10-1.10
t = trace (<0.01%) t tentativeidentification
: = : r a c e( < 0 . 1 % ) * correclisomernot given a also knownas umbellulol
' :,crrectisomernot identified

13
Gi n ger O il o-copaene(0.7%)
linalool(0.4%)
Using a combination of GC/MS and retention indices, a bornylacetate(0.8%)
sample of ginger oil, which was produced from ginger grown neral(1.3%)
in Taiwan,was examinedby Sheenet al. (1992).Theseauthors b o r n e o(l 1 . 1 %)
identified the following constituents: zingiberene + geranial(29.0%)
B-bisabolene (5.8%)
o-thujene(0.21'/") neral(6.04%) o,-farnesene* + geranyl
cr-pinene(4.41%) zingiberene(2.84"/.) acetate(7.3%)
camphene(16.03%) geranial(18.95%) B-sesquiphellandrene (14.0%)
B-pinene(1.10%) B-sesquiphellandrene + ar- geraniol(0.4%)
myrcene(1.15olo) curcumene+ geranyl
lim o ne ne(1 .60 % ) acetate(12.32'/.)
B-phellandrene (6.79%\ citronellol(9.10%) From the analysis of the same oil on the non-polar column,
1,8-cineole (8.86%) nerol(0.05%) the oil was found to contain:
terpinolene (0.24%) geraniol(0.73o/o)
2-heptanol + 6-methyl-s-hepten-cubebolisomer*(0.03%) tricyclene(0.2%)
2-one (0.67%) o-pinene(3.0%)
cubebolisomer*(0.03./")
2-nonanone(0.07%) methylheptenone(0.4%)
a curcumenol* + unKnown
citronellal+ o-copaene(0.52%) sesquiterpeneestet(0.27"/o) B-pinene+ myrcene(0.7%)
2-nonanol(0.13%) B-phellandrene (9.6%)
elemol(0.26%)
linalool(0.80%) linalool(0.8%)
sesquisabinene hydrate.
(0.01%) (0.23'/") borneol(0.8%)
B-elemene
2-undecanone (0.36%) (0.3%)
o,-terpineol
zingiberenol (0.38%)
bornylacetate(0.26'/") nerol(0.2%)
p{arnesene*+ citronellyl neral(1.4k)
acetate(0.38%) geraniol(0.5%)
geranial(1.4%)
geranylacetate(0.9%)
The authors evaluatedthe odor strength ofeach compo- cx-copaene (0.4%)
B-elemene (0.7%)
nent at the exit port of the GC. They found that the main (29.0%)
zingiberene
contributors to the odor of the ginger oil under study were B-bisabolene + u-farnesene*
neral, geranial, B-sesquiphellandrene,ar-curcumene and (14.0%)
geranyl acetate. It is not sulprising that these authors be- 0-sesquiphellandrene (9.9%)
lieved that neral and geranialcontributed to the odor ofthe " correct isomer not identified

oil becausethe amounts identified were considerablylarger


than normally encounteredin ginger oil. Also in 1992,Tanabe It is worth noting that the 1:1 quantitative amounts of
et al. also used GC/MS to analvze an oil nroduced from geranialto neral in any essentialoil is very unusual;neverthe-
freslrh,harvestedrhizomesof a smallJapaneseginger (Zlngiber less,it was explicitly noted that the oils usedin the studywere
o-fficinalet,ar. ntbens Makino). ThL authors th" from authentic sources,although the sourceswere not iden-
nlonoterpene and sesquiterpenecomposition"o*p*r"J
of the "niother rhizome" with the central and
iirst through fourth rhizome branching. A sum- Table lX. The monoterpene and sesquiterpene contents
nran ofthe resultsofthis study can be seenin of Japaneseginger rhizomes
Tabie L\.
\n oii of ginger of Nigerian origin was sub- Branched rhizomes

iected to analysis(Anon 1993) using GC/MS Compound Mother Central 1st 2nd 3rd 4th
anclKor-atsIndices on both a polar and a non- cx,-prnene 31.3- 34.6 22.3 31.7 38.5 4 1.1
polar SCOT capillarycolumn. The compounds campnene 120.9 168.9 102.6 105.2 1 3 5 .6 t r+ 3 . c
identified and the amounts that were found in myrcene 25.9 36.7 23.2 31.0 36.7 37.5
i l . p olar c olum n an a l y s i w
s e re : 50-2 38.4 22.2 42.6 75.7 92.6
B-phellandrene
l.icyclene(0.2%) 1,8-cineole 74.7 76.0 75.1 69.6 85.6 72.9
cr-pinene(3.3%) borneol 13-2 18.3 10.8 14.0 10.4 12.9
camphene (8.8%) neral 190.9 71.6 35.8 42.9 5 0 .3 5 3 .1
3-pinene (0.5%) geranial 295.1 211.9 278.8 294.4 330.1 362.2
sabinene (0.8%)
nyrcene(1.5%) geranylacetate - 4.6 7.9 25.3 59.9 6 4 .1
csphellandrene (0.5%) ar-curcumene 30.8 34.0 21.2 29.5 32.8 34.4
i rmonene+ 1, 8- c in e o(1
l e.7 % ) zingiberene 371.0 662"6 318.1 477.1 6 6 9 .1 723.3
3-phellandrene (8.2%) B-bisabolene 149.5 186.9 124.6 164.4 251"6 266.3
':.:erpinene(0.1%) p-sesquiphellandrene 19 0 . 5 229.9 1 3 1. 4 1 7 7. 3 2 5 6.3 268.4
;-cymene (0.1%)
::':lrolene(0.3%) - ppm
tified. This same year, Demissew (1993) reported that the a{hujene l i nal ool

composition of an oil produced from Ethiopian ginger was: 0-prnene B-caryophyllene


(I-terpinene citronellylacetate
o-pinene(1.00%) geraniol(O.21'/") campnene neral
camphene(3.75%) cital (1.32"k) myrcene zingiberene
limo ne ne(6.5 1% ) ar-curcumene(6.70'/") limonene ct-bergamotene*
lin alo ol(1.5 1% ) zingiberene (35.56%) B-phellandrene geranial
borneol(1.08%) B-bisabolene (12.15%) 1,8-cineole ar-curcumene
citronellylbutyrate(1.O2%) p-sesquiphellandrene(12.32/") terpinolene farnesene*
2-heptanol d a r r n \/l 2noieia

6-methyl-5-hepten-2-one B-sesquiphellandrene
2-nonanone nerol
The following year, Denyer et al. (1994), reported that
citronellal geranyl2-methylpropionate
several sesquiterpenehydrocarbons such as ar-curcumene, ct-copaene elemol
zingiberene,B-bisabolene and B-sesquiphellandrene possessed
antirhinoviral activity (activity against rhinoviruses which are
among those responsiblefor the common cold), the latter of They found that three months after the ginger was irradi-
these being the most active. ated,the amountsof certain componentssuch aszingiberene,
AIso in 1994, Pellerin described the differencesbetween o-bergamotene,neral, geranial and ar-curcumenewere sig-
ginger oils produced from Z. fficinale grown in Australia, nificantly reduced over the same volatiles isolated from non-
India and Sri Lanka. These differencescan be seen in Table irradiated ginger.
X. It is a shame that the author didn't review the study of van This sameyear,Vernin and Parkanyi (1994) compared the
Beekand Leliveld ( 1991) becausehe would haverealizedthat major componentsof Chineseand Indian ginger oil using CC/
the main sesquiterpene hydrocarbons of ginger oil are as
follows: Table Xl. Comparativechemical composition (o/o)
of Chineseand lndian ginger oil
zingiberene
F-bisabolene
(E,E)-o,{arnesene Compound Chineseoil lndianoil
B-sesquiphellandrene cr,-prnene 1.30 1. 40
ar-curcumene camphene 4.65 4.46
Also, it should be noted that zingibene existsonly asa single B-pinene 0.17 0. 12
compound not in cx-and B-forms. sabinene 0.06 0.04
Wu and Yang (1994) compared the volatiles of ginger myrcene 0.57 0. 43
before and after treatment of the rhizomes with y-irradiation. 0. 23
o-phellandrene 0.15
The volatile compoundsthat were monitored by GC and GC/ limonene 0.95 0. 91
\IS were: 2.45 3. 41
B-phellandrene
1,8-cineole 2.07 1. 70
p-cymene 0.06
Table X. Comparativechemical composition
of various ginger oils terpinolene 0.16 0. 13
2-heptanol 0.04 0.36
Australian Indian Sri Lankan 6-methyl-5-hepten-2-one 0.35 0. 17
Compound oil oil oil 2-nonanone 0.02 0"41
camphene 13. 9 t 0.9-14.1 o-copaene t 0.46
p-bisabolene 20.1-60.4 B-elemene 1.15 0. 71
p-bisabolene+ B-farnesene* 2 .1 I t.c 2-undecanone 0.10 1. 43
ar-curcumene 5 .9 18. 9 5.7-27.1 cr,-terpineol 0.80 0.32
pJarnesene* 0.5-1.2 B-caryophyllene 0.50 0.30
p-sesquiphellandrene 3 .1 t-0.3 borneol 2.16 2.82
p-zingiberene 0.3-1.2 zingiberene 38.12 40.20
a-zingiberene 0.1-0.6 B-bisabolene 5.16 6.00
zingiberene 3 .9 7. 4 B-sesquiphellandrene 7.20 7.30
linalool t.3 1. 3 1.0-5.4 ar-curcumene 17.06 17. 08
nerolidol. 1A 1. 6 0.6-1.0 geraniol 0.66 0.50
p-sesquiphellandrol 1. 5 1. 6 0.2-1.2 nerolidol- 0.37 0.41
geranial 5.2 1. 0 1.8-15.3 cls-sesquisabinene
hydrate o.23 0.22
neral 4. O 0.6 2.5-10.1 zingiberenol 0.34 0.30
1.8-cineole 7.5 0. 3 2.1-12.2 trans-B-sesquiphellandrol 0.14 0. 16

: = t r a c e( < 0 . 1 % ) t = trace(<0.01%)
* correctisomernot given
'correct isomernot characterized

15
MS, the results of which can be seenin Table XI. Numerous In 1981, Takahashi determined that ylang ylang oil of
minor componentsthat were also identified were: Reunion origin contained germacrene D (4.67Eo)and mint
nexane aromadendrene sulfide (0.001E")as minor constituents.An oil of ylang ylang,
othujene (Z)-B-farnesene which was produced in Yunnan (China), was reported (Cu
toluene (E)-B{arnesene 1988) to contain the following components:
hexanal 6-selinene
2-heptanone neral cr-pinene (0.01%) (33.00%)
B-caryophyllene
octanal 6-cadinene B-pinene(0.02'/.) cx-humulene(7.69%)
p-isopropylanisole ar-curcumene p-cresylmethylether (2.41%) y-muurolene(19.82%)
5-elemene cis-calamenene methylbenzoate(0.660/0) a bergamotene.(5.40%)
cx-amorphene 2tridecanone linalool(0.41%) B{arnesene(3.29%)
R-nr rhahana germacreneB benzylacetate(0.05%) B-cadinene(1.74"/.)
campnor frans-calamenene
2-nonanol elemol
linalool frans-sesqu
isabinenehydrate
cis-limoneneepoxide 10-epi-y-eudesmol Table Xll. Comparativechemical composition (%)
frans-limoneneepoxide zingiberenol"
isomer of differentylang ylang oils
cls-o-bergamotene o-eudesmol
frans-d-bergamotene B-eudesmol Compound Yunnan Laos Thailand
y-elemene pentenylcurcumene*
(China)
cr-thujene 0 .1 3
0,-pinene 0.01 0.03 0.24
T. A. van Beek and G. P. Le$eld , Isolation and identification of the sabinene 0.26
fiae mojor sesquiterpene hydrocarbons of ginger. Phytochem. B-pinene o.ou o.tt 0.05
Anal.,2, 26-34 (199i). myrcene 0 .5 7
L-Y. Sheen, S-Y. Lin and S-j.Tsai, Odor assessmentsfor oolatile cr-phellandrene 0 .0 1
compoundsof gadic and ginger essentialoils by snffingmethod of 6-3-carene 0.06
gaschromatogrryhA J. ChineseAgric. Chem. Soc.(Taiwan),30, p-cresylmethylether 11.55 2.08
p-cymene 0.64
14-24 (1992).
1,8-cineole 0.01
M. Tanabe,M. Yasuda,Y. Adachi and Y.Kano, Seasonaloariation of
(Z)-B-ocimene 1 .4 5
Jlaaor components in Japanese "Kintoki Ginger." Shoyakugaku (E)-B-ocimene 1 .3 8
Zasshi, 46, 37 -41 (L992).
6-2-carene 0 .1 2
Anon, Analytical Methods Committee, Application of gas-liquid allo-ocimene* 0 .0 7
chromatography to the analysis of essential oils. Par't )l.y'l. linalool 3.28 10.64 6.62
M onographsfor fia e essential olls. Analyst, f f 8, I 089- 1098 ( I 993). methylbenzoate 1.O2
benzylacetate 0.28 0.13
S. Dernissew, A description of some essential oil-bearingplants in
Ethiopia andtheir indigenoususes.!. Essent.Oil Res.,5,465-475
terpinen-4-ol o.,o
o(-terpineol o.o7
( 1993).
methylchavicol 0.09 o.to
C. V. Denyer, P. jackson and D. M. Loakes,lsolationof antirhinoairal citronellol 0.02
sesquite:enesfrom ginger (Zingiber fficinale). l. N at.Prod., 57, geraniol 5.07 1.98 0. 01
658-662(1994). citronellylacetate 0. 02
P. Pellerin, Le gingembre: production et analyse. Parfum. Cosmet.
s-copaene 0"03 o.oa 0. 40
geranylacetate 13.41 13.68 0.30
Arom., (117),70-73(1994).
B-elemene 0.11 o.12
j-j. Wu andJ-S.Y utg,Effects of yirradiation onthe oolatile compounck 25.44 25.68 11. 39
B-caryophyllene
of ginger rhizome (Zingiber fficinale Roscoe). ]. Agric. Food q-humulene 5.54 6.48 2.83
Chem., 42, 2574-2577 (1994). y-muurolene 17.09 15.76 11. 38
s-larnesene* 6.39 4.76 38.72
G. Vernin and C. Parkanyi,Gln ger oil (Zin giber ffi cinaleRoscoe). h:
Spices, Herbs and Edible Fungi. Edit., G. Charalambous, y-cadinene 0.08 0.07 0.20
pp 579-594,Elsevier SciencePubl., Amsterdam (1994). B-cadinene 0.82 0.99 0.83
6-cadinene 0.03
elemol 0.02 0.05
Yl a ng Y lang O il
6-cadinol 0.31 o.22 i,,
farnesol* 3.41 4.69 8.39
In 1966,Vernin reported that ylang ylang oil contained methyl
benzylbenzoate 5.57 9.48 5.29
anthranilate as a trace component. Twelve years later, Ross farnesylacetate* 0.28 0 . 1I t.zJ
(1978)used reversedphaseHPLC on a H1)ersil SAScolumn benzylsalicylate 0.25 0.28
with methanol-water (1:1) as the mobile phase to separate dibutylphthalatet o.uu
methyl anthranilate, benzyl acetate and p-methylanisole in a * correctisomernot given
sample of ylang ylang oil.
16
methylchavicol(0.04%) farnesol*(4.75%)
geraniol(2.48%) benzylbenzoate(5.33%) Table XlV. Comparative chemical composition (o/o)
geranial(0.04%) farnesylacetate*(0.91%) of the different grades of ylang ylang oil
o-copaene(0.51%) benzylsalicylate(0.34%)
geranylacetate(6.21%)
Compound Extra ill
'correct isomer not given
isoprenylacetate o.74 0.42 0.04 0.01
It shouldbe noted that this oil is very atlpical forylangylang prenylacetate 1.59 0.89 0.08 0.02
oil. Based on the above-noted oil composition, it must be cI-pinene 0.23 0.19 0 .1 3 0 .0 8
presurnedthat the oil also possessedan atypical aroma. (Z)-3-hexenylacetate 0.14 - 0 .0 2
This sameyear, Ding et al. (1988) examinedthe composi- hav\rl r^al.+a 0.22 - 0 .0 1
tion ofylang ylang oil produced from three different sources p-methylcresol 8.47 5.75 1 .1 9 0 .3 9
br GC/MS. The origins of the three different ylang ylang
1,8-cineole
+ limonene 0.20 0.17 0 .0 9 0 .0 3
shrubs were Xishuangbanna(Yunnan), Thailand and Laos, methylbenzoate 4.97 3.35 0.70 0.20
altliough the ylang ylang flowers were all harvested from linalool 8.60 7.27 2.56 0.76
transplantedshrubs grown in Xishuangbanna.A summary of benzylacetate 12.36 7 "68 1.68 0.69
the analysesis shown in Table XII. cx,terpineol
+ methylchavicol 0.15 0.13 0 .11 0 .0 2
These same authors also compared the composition of 2-phenethylacetate 0.19 0.12 0 .0 4 0 .0 2
r lang ylang oil produced from the Yunnan ylang ylang from
geraniol 0.29 0.37 0 .4 3 0 .19
ilou'ers picked at different harvestingtimes. The oils, which (E)-anethole 0.36 0.19 0 .1 7 0 .0 9
lr ere produced from green buds, green flowers,green/yellow eugenol 0.08 o.20 0.29 0.06
ilou'ers and yellow flo'uvers,were found to possesscomposi- geranylacetate 4.48 4.26 2.96 1 .2 1
tior"raldifferences as shown in Table XIIL cr-copaene 0.61 0.81 1 .2 2 1 .6 0
In 1992, a commercial report appeared (Benvenisteand B-cubebene + B-elemene 0.41 0.49 0.64 0.54
-\zzo) within which the analysis of the four grades of ylang cinnamylacetate 3.97 2.76 1 .0 9 0 .8 8
riang oil produced in the Comoro islands (Federal Islamic isoeugenol* 0.50 0.50 0.29 0.36
Republic of Comores) could be found. The four commercial 5.18 8.04 12.90 12.39
B-caryophyllene
s-radesof ylang ylang oil are: Extra (first fraction, ca. I57o), B-cedrene 0.14 o.20 0.37 0.46
Crade I (secondfraction, ca. I57o), Grade II (third fraction, o-humulene 1.76 2.67 3.35 3.62
prenylbenzoate 0.82 0.11 0 .2 5 0 .2 7
TableXlll. Comparativechemical composition (%) of germacreneD 17.07 20.11 21.71 21.65
ylang ylang oil produced trom s-farnesene* 8.17 10.69 15.73 23.75
flowers harvested at different flowering times y-cadinene 0.64 0"78 1 .1 3 1 .2 5
6-cadinene 1.14 1.68 3 .1 2 3 .6 7
Compound yellow- isoeugenylacetate* o.12
yellow green green green T-amorphol 0.82 1.12 2 .0 0 1 .9 3
flowers flowers flowers buds
(Z,Z)- a-tarnesylacetate 1.31 1.60 2 .O2 1 .5 6
p-cresylmethylether 3. 40 1. 70
linalool benzylbenzoate 4.83 5.83 6.33 5.43
methylbenzoate 1. 19 0. 22 0.0 1 (E,E)-a{arnesylacetate 1.68 1.89 2 .7 0 3 .4 6
benzylacetate 0.05 benzylsalicylate 2.37 2.63 3 .0 5 2 .8 1
methylchavicol 0.05 0.01 * correctisomernot given
geraniol 0.52 2. 45 1. 20 0.2 1
c{-copaene 0.04 0.06 0.04
geranylacetate 2. 58 7.28 4.69 2.37
B-elemene 0.70 0.23 0.22 0.32
p-caryophyllene 31. 33 26.46 37.06 47.95 ca. 23Vo), and Grade III (fourth fraction, ca. 477o). The
cr-humulene 8. 35 6. 64 9. 28 11 . 6 8
'1-muurolene 13. 28 20-94 19.34
analysespresented in this report can be fbund in Table XIV
13.96
ciJarnesene* 9. 21 8. 09 10. 86 9.8 6 One year later, Stashenkoet al. (1993) analyzedoils pro-
lcadinene 0.40 0.34 0.23 0.26 duced from freshly hawested mature yellow ylang ylang
B-cadinene 1. 90 2.26 2.05 2.70 flowers, petals and ovaries of Colombian origin that were
6-cadinene 0.04 steam distilled for either I or 2 h. Usinq a combination of
6-cadinol 0.68 0.90 0.84 0.77
farnesol*
modern analyical techniquessuch as GC (KovatsIndices on
o.z5 4.52 3.99 2.34
benzylbenzoate I J.JJ 9.26 5.07 3.56 a DB-1 column), GC/MS, IR, ]H- and l3C-NMR they were
farnesylacetate* 2. 48 0. 79 0. 58 0.3 6 able to identifv more than 50 constituents in the oils. A
benzylsalicylate 0. 77 0. 44 0. 22 0.1 0 summary of these results can be seen in Table XV
dibutylphthalatei 1. 77 0.65 0.26 0.34
C.Yernin,Ddtectionet dtaluationdel'anthranilatedemethqlet deses
'correct isomernot given cldriuds naturelsetde.sqntlrcse
methylestlansdiffdrentdchantilltnts
artilact par CCM et CLC. La Franceet sesPa#urns, 9, 429-448(1966).

\7
M.S.F. Ross, Application of high-performonce
Iiquid cLrrorntography to the anahl sisof aolatile
oils. J. Chromatog., 160, f99-204 (1978). Table XV. Comparativechemical composition
K. Takahashi,S. Muraki and T. Yoshida,Sqnthesis of Colombianylang ylang oil
antl distributittn ,'f , -rplnlsulphide.- a nouel
utlfur- containin g sesquiterpene. Agric. Biol. Compound 1 2
Chem.,45, 129-131(r981).
3-hexenol* 0.05
J-Q C", Iunnan - The kingdom of essentialoil 2-hexenol* 0.11 t 0.41 0.04
plants. In: Flaaors and Fragrances: A World
2-methyl-3-buten-2-ol 0.35 0.20 0.03 t 0.07 0.03
Perspectioe.Edits., B. M. Lawrence, B. D.
Mookherjee and B. J. Willis, pp 23I-241,
3-methyl-2-butenol 0.07 t 0.08 0.07 I-

ElsevierSciencePubl. B.V..Amsterdam(1988). 1.96 1.19 1.70 0. 55


camphene 0.04 t 0.04 t 0.03 0. 01
J-K. Ding, Y-F.\|Z-H. Ding, H-D. Sun,Z-G. Liu
and S-H. Dao,studies onthe constituentsof the B-pinene 0.35 0.41 0.53 0.38 0.22 0.52
essentiul oils from Cananga odorata in the myrcene 0.13 0.09 0.17 0.09 0.13 0"05
different uarieties and the Jloutered periods. 3-hexenylacetate- o.41 0.08 o.17 0.09 0.13 0. 05
Acta Bot. Yunnanica,10, 331-334(1988). p-methylanisole 9.01 2.06 3.57 0.44 2.82 2.40
B. Benveniste and N. Azzo, Ylang Ylang. Kato 2-hexenylacetate. 0.18 0.11 0.11 0.08 0.11 0. 08
Tet'hnicalBuIletinandN er,rsletter.Vol VI. Iune '1,B-cineole 0.68 0.35 0.17 t 0.14 0. 09
30, Kato Worldwide Ltd., Mouni Vernon, NY
( 1992). limonene 0.12 0.06 0.09 t - 0.08
benzylalcohol o.77 0.64 0.10 t 0.03 0.04
E. Stashenko,J. R. Martinez, C. Macku and T. (E)-B-ocimene 0.66 t t- 0.33 r
Shibamoto, HRCC and GC-MS anahrsis of
methylbenzoate 4.15 2.19 1.51 0.17 4.44 1. 87
essenliul oil from C,,lombian ylung- ylung
linalool 29.23 15.01 20.81 4.55 24.73 5.87
(Canango odorata Hook.fil. et Thomsort,forma
benzylacetate 4.64 4.57 1.34 0.35 11.73 3.78
genuina).J. High Resol.Chromatog.,L6,44L-
444 (1993). cihrrlhcnznaic 0.95 0.67 1.53 0.43 0.23 0.08
methylsalicylate 0j2 t t- 0.11 t
crterpineol O.22 0.13 0.15 0.03 0.01 t
2-phenethylacetate 0.15 0.11 0.10 t 0.32 0. 13
geraniol 0.25 0.13 o.24 0.21 0.28 0. 12
anethole. 0.47 0.44 0.59 0.52 0.54 0.32
geranylacetate 3.87 3.17 4.48 3.01 5.07 4.57
cI-copaene 0.90 1. 15 0.82 1.08 0.32 0.82
o-ylangene 0.83 0.87 0.91 0.97 0.50 0"89
cinnamylacetate 1.46 1.53 2.03 2.52 3.33 4. 19
p-caryophyllene 6.26 7.91 6.62 8.06 4.25 7.20
cx-ceorene 0.22 0.26 0.23 0.92 0.21 0. 94
cr-humulene 2.01 2.68 2.22 2.56 1.78 3. 00
r-cadinene 0"31 0.34 0.29 0.55 0.62 0.75
methyleugenol 0.20 0.20 0.22 0.52 0.60 0.55
germacreneD 7.71 23.77 21.52 25.70 11.90 20. 98
Y-muurolene 0.24 0.65 0.59 0.64 0.31 0.49
a-amorphene 0.19 0.35 o.24 0.33 0.13 0. 22
(E,E)-o,{arnesene t.o/ c-c I 7.38 7.98 1.18 3. 14
6-cadinene 3.36 0.44 0.43 0.69 0.35 0.39
y-cadinene 0.55 1.27 0.85 1.23 0.48 0.77
caramenene 0.19 0.14 0.31 0.21 0.20 0. 11
(E)-nerolidol 0.32 0.16 0.28 0.20 0"50 0-28
cr-bisabolol 0.19 0.08 0.07 t t-
cedrol 0.32 t 0.54 0.18 0.28 0. 19
6-cadinol o.27 0.16 1.14 0.06 1.08 0. 63
0-cadinol 0.37 0.19 0.s0 0.97 0.24 0.37
T-cadinol 0.20 0.46 0.15 1.00 0.15 0. 41
T-muurolol 0.14 0.40 0"07 0.62 0.17 0. 40
(E,E){arnesol 0.97 3.98 0.93 3.40 2.02 3.21
benzylbenzoate 4.87 12.30 6.07 14.45 11.90 19. 90
(E,E){arnesylacetate 0.82 1.83 0.96 4.45 0.72 1. 86
benzylsalicylate 0.22 O.27 0.33 1.79 1.39 2. 60
t = trace(<0.01%)
* correctisomernot given

1B
Progress in Essential Oils
Reprinted
fromPerfumer
& Flavorist,
May/June
1995,Vol.20,No.3,P.67

ThymeOil 1992).A summary of the results of this study can be seen in


In 1985, Bestmann et al. used both GC and GC/MS to Table II. Theseresultsshowthat there is a fairlywidevariation
compare the chemical composition of a CO, extract of Thy- in the composition of these oils, although none would be
mus aulgaris L. with that of a steamdistillateof the sameplant acceptableas commercial thyme oils.
material and a commercial sampleof red thyme oil produced A year later, Piccaglia and Marotti (1993) examined the
from Z zygis L. A summary of the results of that study are composition of thyme oil produced from Z au,lgari,sgrown in
found in Table I. The authors also noted that there were a Casolavalsenio,Italy, over two seasons.The oil, which was
number of high molecular weight compounds (greater than
I}Va) in the CO, extract.
Table L Comparativechemical composition of two
The enantiomeric distribution of isomers of the borneol thyme oils and a CO, extract of thyme
and isoborneol in five samplesof thyme oil were found by
Kreis et al. (1991)to be: Steam Red thyme
1S,2R,4S-(-)-borneol(87.5-87.8%): Compound CO2extract distillate oil
1R,2S,aR-(+)-bo"neol(12.2-12.5%),
1R,2R,4R-(-)-isoborneol
(20.9-21.2ok): (78.8-7
1S,25,45-(+)-isoborneol 9.1%). tricyclene t 0.08
In 1991, Piccagliaand Marotti examinedthe composition a,-thujene 0.03 0.36 0.04
o-pinene 0.01 0.96 0.3 0
of ar.vildform of7. au,lgariswhich was grown in an experimen- campnene 0.04' 0.49 1.97
tal garden in northern Italy. Using GC and GC/MS as their sabrnene I I
methods of analysis,the authors analyzed an oil produced B-pinene 0.35 0.15 0.08
from clonally reproduced plants that were harvestedat the myrcene 0.17 0.86 1.58
samedevelopmenttime over two consecutiveyears.The oils
cx-phellandrene 0.09 0.08 0 . 14
6-3-carene 0.02 0.06
were fbund to possessthe follor'vingcomposition: o-terpinene 0.07 1.03 0.06
cr-humulene(0.13-0.23%) p-cymene 2.55 18.88 37.74
crthujene(0.87-2.10%)
cr-pinene(0.49- 1.34%) (Z)-B-farnesene (0.03-0.04%) limonene 0.09 0.57 3.09
camphene(0.18-0.46%) "y-muurolene(0.04-0.07 %) 1,8-crneole 0.16 0.25 0.27
sabinene(t) p-cymen-8-ol(trace) Tterpinene 0.67 6.37 4.41
o/") o-terpineol(0.17-0.26'/") terpinolene 0.09 0.16 0.40
B-pinene(0.17-O.41
1-octen-3-ol(0.41-0.67%) methylthymol (1.43-1.52%) linalool t.oJ 1.48 9.42
myrcene(1.40-2.1 4o/o) thymoquinone (t) pinocarveol* 0.o2 0.01
o,-phellandrene(0.15-0.19%) bornylacetate(0.04-0.07%) B-terpineol. 0.22 0.24 u. t o

crthujone(0.00-0.51 %) thymol(16.55-38.24%) borneol 0.02 0.28


carvacrol(1.61-1.72%) terpinen-4-ol 1.04 0.87 0 . 16
B{hujone(0.00-0.15%)
camphor(t-0.30%) cuminylalcohol(t-0.08%) crterpineol 0.20 0.15
borneol(0.44-0.45%) o-copaene(t-0.03%) methylthymol 0.32 0.53
terpinen-4-ol (0.98-1.1
0%) B-bourbonene (t-0.03%) methylcarvacrol 0.54 0.55
5-3-carene (0.07-0.
13%) lene (2.38-4.28'/') geraniol 0.04
B-caryophyl
nene (1.67-2.34%)
o(-terpi lorene(t-0.10olo)
viridif bornylacetate 0.37 o.24 0.07
limonene(0.17-0.30%) cr-muurolene (t-0.08%) thymol 36.59 48.26 30.90
p-cymene(18.60-25.34olo) 1-cadinene (0.06-0.15%) carvacrol 3.17 5.54 5.87
1,8-cineole (1.96-2.26%) 6-cadinene (0.11-0.25%) d,-yrangene I I

yterpinene(12.06-12.27%) caryophylleneoxide(0.29- o-copaene 0.22 0.12


terpinolene (0.18-0.19%) 0.45"/") B-caryophyllene 1.64 3.13
linalool(2.42-2.82Y") 6-cadinol(t-0.09%) cr-humulene 0.09 0.12
(1-0.04%) cr-cadinol(t-0.05%) vatencene 0.01
B-gurjunene y-cadinene
(t-0.03%)
aromadendrene o.24 0.34
hexadecane 0.10 0.02
heptadecane 0.27
palmiticacid 5.98 o.14
An oil produced from T. aulgaris produced in Poland was
heptadecanoicacid 0.16 I
found (Kurowska et al. 1991), not unexpectedly,to contain stearicacid 8.30 0.27
thymol (31.4ECand p - cymene (36.47o)asm ajor constituents.
t = trace(<0.01%)
Thvme oil oroduced from five different areas in eastern * correctisomernot identified
Liguria (Italy)was analyzedby capillary GC (Maccioni et al.

19
produced from plants harvested in full flolver, was analyzedby
both GC and GC/MS. The comoosition of both oils was as Table ll. Comparativechemical composition
of thyme oils produced from various locations
follows:
in eastern Liguria
o{h ujene (0.87-2.10'/.) terpinolene (0.18-0.19%)
cr-pinene (0.49-1.34%) linalool(2"42-2.82k) Monte Punta Monte Gapo
camphene(0.18-0.46%) a-thujone(0.00-0.51 %) Compound RoccheitaCorvo Marlo Acqua Zezziggiola
sabinene(t) B-thujone (0.00-0. 15%)
(0.1 7-0 .41 % ) camphor(t-0.30%) o-prnene 0.92 1. 2 1 1. 15 1.64 1.3 1
B -pin en e
1-octen-3-ol(0.41-0.67%) borneol(0.44-0.45%) campnene 1. 11 2.16 1. 1 4 1.48 2 .3 1
myrcene(1.40-2.14'/") terpinen-4-ol (0.98-1"10'l") B-pinene 0.22 0.27 0.22 0.34 0.36
o-phellandrene (0.15-0.19%) p-cymen-B-ol(t) myrcene 1.71 1.47 1.62 2 - 29 1 .4 7
6-3-carene(0.07-0.13%) crterpineol(0.17-0.26%) limonene 0.33 0.48 0.86 0.37 0.37
methylthymol (1.43-1.52'/.) B-gurjunene (trace-0.04%) 1.8-cineole 0.23 1.13 0.62 0.84 2.54
thymoquinone (t) aromadendrene (t)
bornylacetate(0.04-0.07%) o-humulene(0.13-0.23%) yterpinene 11.O7 11.00 13.10 1 7. 1 7 1 0 .5 3
thymol(16.55-38.24'/.) (Z)-B{arnesene (t-0.04%) p-cymene 17.01 22.02 17.50 24.68 26.31
carvacrol(0.61-1.72'/") o,-muurolene(0.04-0.07'/") camphor 0 . 13 0.20 0.12 t 0.34
cuminylalcohol(t-0.08%) lorene(t-0.10%)
viridif linalool 0.44 0.30 0.65 0.75 0.78
c{-copaene(t) y-muurolene (t-0.08%) bornylacetate 2.34 1.93 0.81 0.41 1.19
B-bourbonene (t) y-cadinene (0.06-0. 15%)
B-caryophyllene0.38 0.19 0.34 1. 2 0 0 .16
B-caryophyl lene (2.38-4.28%) 8-cadinene (0.11-0.25%)
s-terpinene(1.67-2.34%) caryophylleneoxide cr{erpineol 1.26 0.23 0.16 t 0.32
p-cymene(18.60-25.34%) (0-29-0.45%) 2.59 2.44 5.02
borneol 1.35 4.55
lim on en e(0.1 7-0 .30% ) 6-cadinol(t-0.09%) geraniol 0.39 0.28 0.39 ti
1.8-cineole (1.96-2.26"/") cr-cadinol(t-0.05%)
thymol 31.39 11.33 36.66 17.31 1 0 .9 5
7te rpinene (12.06-12.27'/")
carvacrol 12.36 27.95 5.79 18.88 23.29
i = t r a ce (<0 .0 1 %)

t = trace(<0.01%)
It should be noted that these oils could not be used
conrmerciallv because of the lorv thyrnol content and the
richness of y-terpinene and p-cymene. 6-3-carene(t) cxterpinylacetate(0.25'/.)
Thirt same year, Salgueiro et al. (1993) analyzed an oil of Z myrcene(0.52%) oterpineol (0.27%)
: 111lsssp.:ygis of Portuguese origin using GC. The oil compo- (E)-B-ocimene (O.92"/") geranylacetate(0.35%)
rerrts. u-hich were mainly identified by retention times, rvere limonene(t) geraniol(0.18%)
(t)
1,8-cineole allo-aromadendrene (t)
l,-.rtinclto be:
y-terpinene
(0.93%) p-cymen-8-ol (0.68%)
cr-thujene (0.8%) linalool(3.8%) p-cymene(10.34%) thymol(74.00%)
u-cinere (0.7oo) bornylacetate(t) frans-sabinene hydrate(0.12o/o) carvacrol$.90'/4
carphene (0.6%) B-caryophyllene (1.5%) camphor(0.24eo)
:-c'nene(0.1%) terpinen-4-ol (0.9%) t=trace (<0.01%)
sacinene(t) cr-humulene (t)
-r''cene (1.3%) g-terpineol (0.1%) Furthermore, the authorsfound that this thymol chemofpe
r:r-rerpinene (1.07o) borneol(1.0%) ofT. zygis possessedanti-hepatotoxicactivity and free radical
-onene (0.4%) germacrene D (t)
scavengeractivity.
' 3-:ire ole(O.2o o) (t)
B- bis abolene
..-:erpinene (1s.0%) geranylacetate(0.2%) Thy mus oul gads, that was harvested in the wild in Italy was
r-.t,nene (19.9%) geraniol(0.3%) water distilled (Perrucciet al. 1994)to produce an oil thatwas
::rc rclene (t) thymol(0.2%) analyzedby capillary GC using retention indices asthe method
3-:c:anol(0.1%) carvacrol(42.0%) of componentidentification.The compounclsidentified in the
'-:c:en-3-ol(0.2%) caryophyllene oxide(0.6%)
oil were:
: ' ais-sa bin en eh yd r at e( 0. 2% ) ( 0. 1% )
v ir idif lor ol
:a- :-cr (0.5 0o ) (1.15%)
cr-pinene linalool(t)
<i.l ".) camphene(2.2170) bornylacetate(t)
B-pinene(t) B-caryophyllen e (1.46%)
Tlrrs is an erample of the carvacrolchemotype of T.zygis myrcene(1.35%) o-terpineol(t)
ssf-,::i:ii and not the thymol chemotlpe which is the raw limonene(t) borneol(4.60%)
1,8-cineole(2.56'/") geraniol(t)
n^:treri:Jused to produce the commercial red thyme oil.
y-terpinene(9.15ol.) thymol(7.30%)
d'o iri 1993,Jimenez et al. {bund that an oil of T. zygis oI p-cymene(31.19%) carvacrol (28.34%)
Spanishoriqin contained the fbllowing constituents: camphor(t)
t=trace(0.01%)
o,-tf,jjene(t) linalool( 0. 16% )
a-pirene(0.40%) Iinalylacetate(0.22%)
camp .en e(l) (t) Basedon the abovecomposition,it is obviousthat this oil
B-caryophyllene
sabinene(t) terpinen-4-ol(2.32'/.) is not related to those found in commerce.
(0.1 0% )
B - pin en e borneol(t)

20
Using :i combination of GC and GCIMS, the oil of I In 1990, Sugimura et al. used both GC and GC/MS to
ttigari,s that has become naturalized in Nerv Zealand was compare tlie chemical composition of three cultivars of
reported (McGimpseyet al. 1994)to contain: patchouli. One cultivarwasobtained from Tairvan(cultivar I),
s-thu jen e(0 .1-1 .1%) the secondone ii-omthe Philippines (cultivar II) and the third
borneol(1.2-4.7%)
c-p ine ne(0 .1-1.1 % ) terpinen-4-ol (0.4-0.7%) one (cultivar III) from Japan.The authors determined that
camphene(0.2-1.6%) cr-terpineol (0.3-0.7 %) the biomassyield per plant, the oil vield per plant and tlie
B-pinene(0.5-1.2o/") methylcarvacrol(O.a'a.0%) percent oil yield were as follows:
myrcene(0.8-2.1%) methylthymol(0.9-2.8%)
p-cymene(19.8-55.9%) thymol(9.5-37.4%) Biomassyield Oityietd Oil
lrmonene + 1,8-cineole ( 1. 5- 11. 0%)
c ar v ac r ol perplant perplant yield
(2.2-4.2o/o) (1.5-3.8%)
Cultivar (S) (S) (t")
B-caryophyllene
T-terpinene (1.9-19.1%) germacreneD (0.3-12%) | 26.8 0.43 1 .6 0
linalool(2.7-5.5%) caryophyliene oxide(0.5-1.9%) ll 27.2 0.27 0.99
camphor(0.4-1.3%)
ilt 140.6 t.oo '1.1 8
it is worth noting that the authors are pursuing the potential Horvever, the trichome density (number of essential oil
of establishing this or othe r Thymus utlgarls accessions as the glands per leaf) was greatest for crrltir-ar I ancl lorvest frrr
brrsisfor commercial production of thyme oil in the semi-arid cultivar III. The chemical composition obtained from oils
region ol'central Otago (Nerv Zealand). produced from the three cultivats be seen in Table III.
"an
H. J. Bestmann,f . Erler and O. Vostrorvlg',Ertraktion utn Thynian In 1992, Hasegar,vaet al. characterized germacrene B as a
rnit fli.issigernC02 in Labo,nnasstrLb.Zeit. Lebersmitt. Unters constituent of'patchouli oil. Usirrg oil obtained from the
Forsch.,180" 491-493(19S5). above-noted cultivar II, the iruthors were able to demclnstrate
P. Kreis, D. juchelka, C. Motz and A. MosandI,Chirale inhaltsstoffe the Cope rearrangernent of germacrene B to y-elemene and
iitherischerOla. Deutsch. Apoth. Ztg., l3l, l9B4-19E7(1991): shor'vhou' to pre'r'ent it during patchouli oil analysis.
R. Plccagliaarxl \{. Nlarotti, Conrytositionof the e,ssential
oil of an Analysis of the basic {raction of'patchouli oil using prepara-
Italiur Thyrrntsxulgaris L. ecotype.Flav. Fragr. 1., 6,211-214 tive GC, ltt-NVn
(19e1). and MS, Maurer and Hausei (1992)
characterized the presence of four sullstituted pvridines in
-{. Krrrolr'ska,D. Kalernba, J. Gora and T. Majda, Aralr1sis of essential the oil. The con'rpounds identified were:
oils, a,spectsof their inJhtcnceto insects.Paft IV.'Esserrtial oil of
garrlenthqme(Thqnu,satlgard,sL.). Pestycvdy,(2), 25-29 (1991). (Z)-3-(l-butenyl)
pyridine (Z)-3-(t-butenyt)-4-propytpyridine
S. \Itrccioni, G. Flamirii, P. L. Cioni and P. E. Tomei, Le Tipologie (E)-3-(l-butenyl)
pyridine (E)-3-(l-butenyt)-4-propytpyridine
fitochinLicLrc in Alcunepopolazionidi Thytnts u.tlgnrisL. p resenti
uLl promontorio del Caprione (Liguria Orientale). Rir.ista Ital. Although the authors did not present qualitative data, it is
E PPOS.';'. I3 -18 119927. saf'eto say that the four cornpounds rvere present only in ppm
R. Piccaglia and NI. Nlarotti, Characterization of su;eral oronuttic levels.
plantsgrcrcninnofthern Itolll.Flav. Flagr. J..8. 115-122(1993). Also in 1992, Mookherjee et al. reported on the character-
L. R. Salgueiro,A. Proengada Cunha and J. Paiva,Clrcmotoxonornic ization of a number of new constituents in patchouli oil. The
clmracterization of a Thynus hrlbridfrom Poflugal. Flav. Fragr. r r e w l y i d e n t i f i e d r . o m p o n e n t s r , re r e :
J. , 8, 32 5-3 30( 19 93 ) . guaiolpyridine
T.Jirnenez,M. C. Navarro,NL P.lvlontilltr,A.Maftin, andA. Martlnez, dehydroguaiolpyridine
lhynus ;qgis oil: its fficts ot'tCCll - ind,ucedhepatotoricityand 1,2-dimethylcyclohex-1
-en-3-one
-free-radir:ttlscal)engeractiuittl. J. Essent. Oil Res., 5, 153-155 (syn.2,3-dimethylcyclohex-2-en-1
-one)
( 1993).
T 1,2-dimethylcyclohex-2-en-4-one
S. Perrucci, F. Nlancianti,P. L. Cioni, G. Flamini, I. Morclli and G. (syn.3,4-dimethylcyclohex-2-en-
1-one)
Macc}rioni, ln, xitro antifintgal actixity of cssentktl oil,s against 1,5-dimethylcyclohex-1
-en-3-one
so_nei,solatesof Xtlicrospo,nnrL conis and MicrosporurL glJpseunt. (syn.3,6-dimethylcyclohex-2-en-1
-one)
Plant NIed.,60, 184-r87(1994). rsophorone
J. A. McGimpsel', VL H. Douglas,J. W. r'an Klink, D. A. Beauregard (syn.3,5,5-trimethylcyclohex-2-en-1
-one)
and N. B. Perw, Seusonal uoriatiort in essential oil tliekl and. 1,5-dimethylcyclohexa-3,6-dione
compo sitionfrom naturalized Tlty ntus aulgad.sL. in N er Zealantl.. (syn.2,6-dimethylcyclohexa-1,4-dione)
Flav. Fragr.J.,9,347-352(1994). 1,5,5-trimethylcyclohexa-3,6-dione
(syn.2,6,6-trimethylcyclohex-2-en-1,4-dione)
Pa tchouliO il 1,2,5,5-tetramethylcyclohexa-3,6-dione
(syn.2,3,4,4-tetramethylcyclohex-2-en-1,4-dione)
Using a cornbinationof GC/MS, GC-FTIR and a GC-sniffing
B-patchoulone
procedure, Nikiforov ei al. (1988) determined that the con- s-patchoulone
stituentsof patchoulioil thatpossess
the mostintensepatchouli- 5-oxopatchoulol
lrKeilrotta were: s-guarenone
,tr patchoulol o-bulnesene
0,-cedrenal

(x-guarene norpatchoulenol Furthermore, the authors noted that the components of


o,-patchoulene PUguDrvl patchouli oil that are responsible fbr its characteristic odor.
seychellene are:

27
patchoulialcohol cr-guarenone
norpatchoulenol -en-3-
1,2-dimethylcyclohex-1 Table lll. Comparativechemical composition (%)
of three cultivars ol Pogostemon cablin
nortetrapatchoulol isophorone
p-patchoulenone l,5,5trimethylcyclohexa-3,6- Gompound I illillv
drone
(-cedrenal 6-elemene t.bv 1.34 1 .O2 1 .8 8
0-copaene - 0 "5 4 3 .1 7
TLresane vear,Guan et al. (1992)studiedthe composition cr-guaiene+p-caryophyllene 17.37 13.99 5 .0 6 1 6 .5 8
o,-patchoulene+ 6-guaiene" 12.32 8.93 6.55 14.02
iCLrirese patchouli oil using GC/MS. They found that the
R-natchorrlcnc 0.91 0.63 0 .5 1 1 .0 8
:l cantailed: cx-humulene 0.57 0.62 0.36 0.74
Fnethyl-2-pentanone(0.01%) verbenone(0.02%) longifoleneb 2.72 1.72 18.36 2.27
rexanal(0.01%) myrtenol(0.02%) guaiene* 18.80 13.21 2.BB 14.44
i..nethyl-2-hexanone(0.01%) perilla ketone(0.02'/.) norpatchoulenol 1.08 0.11 0 .0 8 0 .5 8
o-plnene (0.09%) thujone-(t) patchoulialcohol 29.07 22.83 19.02 29.03
camphene(t) 8-elemene(0.04o/")
1-hepten-3-ol (0.01%) (6.91%) Legend: | = Cultivarfrom Taiwan
B-patchoulene ll = Cultivarfrom The Philiooines
lpinene (0.26%) B-caryophyllene (3.1B%)
ll = Cultivarfrom Japan
rimonene(0.02%) cx-guaiene (8.82%) lV = Commercialsamoleof Patchoulioil
rinaiooloxide. (t) seychellene (9.58%) a also knownas B-bulnesene
;inalool(0.01%) cr-patchoulene (8.48'/") b probablyseycfrellene not longifolene
* correctisomernot identified
isophorone(0.03%) B-maaliene (0.66%)
fransverbenol(0.03%) 6-9uaiene(8.65%)
4-methyl-1 Juranyl-1 -pentene y-selinene (0.11%)
(0.0 1% ) ar-curcumene (0.21'/.)
sopinocamphone (0.01%) patchoulialcohol(31.86%)
terpinen-4-ol(0.01%) pogostone(3.83%)
dihydrocarvone.(0.01%) aristolone(0.85%)
' .oqect isomer not identified
:=lne (<0.01olo)

Y. Sugimura,Y. Ichikawa,K. Otsuji, M. Fujita, N. Toi, N. Kamata,R.


The identifications of the substituted furanylpentene, M. del Rosario, G. R. Luingas and G. L. Taga-an, Cultioarietal
pgostone and aristolone require corroboration before they comparis on of p atchouli plant s in relation to essenti aI oil 7sro da ction
can be acceptedas true patchouli oil constituents. and quality. Flav. Fragr. J., 5, 109-114(1990).
\Iore recently, Betts (1994) determined that by using a Y. Hasegawa, K. Tajima, N. Toi and Y. Sugimura, An aclditional
n,etlrl-polvsiloxane capillary stationaryphasecontaining about constit:uentoccurcing in the oil from a patchouli cultiaar. FIav.
Fragr.J., 7, 333-335(1992).
6-r branched aliphatic side chains with L-valine in diamide
B. Maurer and A. Hauser, Neuupyridine deriaati.aesfrom essential
Lin}aqe (Chirosil-Val), the sesquiteryene hydrocarbons in
oils.Chimia,46, 93-95(f992).
patchouli oil are better separatedthan they are by using an
B. D. Mookherjee, R. W. Trenkle and R. A. Wilson, New insightsin
rmtreated methyl polysiloxane column. The oil was found to
the three mast imp ortant natural fragrance p roducts: u;ood, amber
ctntain: and musk. In: Proceedings of 12th International Congress of
$-patchoulene(1.7%) seychellene (6.9%) Flaaours, Fragrances and Essential Oils. Edits., H. Woidich and
o-gurjunene(3.9%) cr-patchoulene(6.4%) G. Buchbauerl Vienna, Austria (1992) pp 234-262.
lene (4.7'h)
rLcaryophyl cr-bulnesene(12.0'/.) L. Guan, L-H. Quan and P-H. Cong, Study on chemical constituents
u-guaiene(10.4o/") patchoulialcohol(28.5%) of aolatile oil from PogostemnnCablln (Blanco) Benth. Tianran
Chanwu Yangui Yu Kaifa, 4(2), 34-37 (1992).
\ \ildlbrov, L. jirovetz, G. Buchbauer and V. Raverdino, GC- T. j. Betts, Eaafuation of a "Chirasil-Yal" caplllary for the gas
FTIRand CC-MS inod,ou.ranalysisof essentialoils. Mikrochim chromatogra:phyof oolati,leconstituents including sesquiterp enes
-\cta Vie nn a), (11 ) , 193- 198( 1988) . in patchouli oll. J. Chromatog.,664, 295-300 ( f 994).

22

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