American Journal of Anal yt ical Chemistry, 2011, 2, 258-261
doi:10.4236/ajac.2011.22031 Published Online May 2011 (http://www.SciRP.org/journal/ajac)
Studies on the Components of Essential Oil of Zanthoxylum
armatum by GC-MS
Amran Waheed, Shahid Mahmud, Mubeen Akhtar, Tanzeela Nazir
Applied Chemistry Research Centre PCSIR Laboratories Complex, Lahore, Pakistan
Received December 16, 2010; revised April 28, 20 1 1; accepted April 29, 2011
Abstract
The essential oil of Zanthoxylum armatum was extracted through hydro distillation and analyzed by GC-MS.
Hydrocarbon fraction (17.35%) of the oil was much lower and oxygenated compounds comprised fairly high
portion of essential oil (39.21%). Percentages of monoterpenes and sesquiterpenes found were 47.33% and
10.83% respectively. Oxygenated monoterpenes comprised major profile of chromatogram of essential oil of
Zanthoxylum armatum i.e. 37.23% where as monoterpene hydrocarbons were 10.09%. Alcoholic percentage
was much higher i.e. 26.76% and 15-hexadecanoloide (6.58%) the only cyclic ester was found in relatively
high percentage.
Keywords: Essential Oil, Zanthoxylum armatum, Gas Chromatography-Mass Spectrometry (GC-MS)
1. Introduction
Family Rutaceae is a large botanical family [1] which
comprises about one hundred and fifty genera [2] dis-
tributed in tropical and temperate region of the world
[3-5]. From economic point, Rutaceae is an important
family. Zanthoxylum armatum locally known as timber
[6-9] is a wild species which is native to Laran Pass in
Dir, Murree, Saidpur, Hazara, Kalapani, Jhelum and Swat
valley. Hard thorny dense tree [10] of Timber is nor-
mally available on banks of Lilly streams and rivers.
The fruits and seeds are employed as an aromatic tonic
in fever, dyspepsia, carminative, stomachic, anthelmintlc
and expelling roundworms [11-13].The volatile oil is
employed as an antidiarrehal, antiseptic, deodorant and
anticataerhal [14-16]. The oil has a good tenacity and is
appreciated for its fixative qualities. Almost all parts of
the plant are aromatic and hence, supposed to possess
essential oil. The essential oil composition can provide
much more knowledge regarding the medicinal proper-
ties and active constituents of this plant [14].The phar-
maceutical companies generally use timur fruit for mak-
ing different types of toothpaste [17].
An examination of literature shows that a lot of work
has been done on essential oils of family Rutaceae
[18-20] but work on the essential oil of this species is
very few [12,16,21].The present study deals with the
chemical analysis of essential oil of wild collected timber
seeds and is part of our screening programme of Pakistan
wild aromatic flora.
2. Metarials and Method
2.1. Extraction of Essential Oil
The mature seeds of Zanthoxylum armatum, was col-
lected from Balakot Mansehra (N.W.F.P Pakistan) and
crushed for hydro distillation. The essential oil was ex-
tracted from distillate with diethyl ether: hexane mixture
(1:3 v/v). Solvent mixture was removed by vacuum dis-
tillation.
2.2. Gas Chromatographic Analysis
Gas chromatographic analysis was carried out on Shi-
madzu GC-14A chromatograph equipped with flame
ionization detector fitted with 25 m × 0.22 mm (id.)
SE-30 capillary column at carrier gas flow rateof 2 ml/min
with split ratio was 1:100 and sample size 0.2 l. The
column temperature was programmed at 70˚C for 4 min.
with 4˚C/min rise to 220˚C while detector and injector
temperature were maintained at 300˚C and 220˚C re-
spectively. Percentage composition of individual com-
ponents was calculated on the basis of peak area using
Shimadzu C-R4A chromatopac electronic integrator.

A. WAHEED ET AL.259
2.3. Mass Spectrometry
Jeol model JMS-AX505H mass spectrometer combined
with Hewlett Packard 5890 gas chromatograph was used
for GC-MS analysis. The essential oil was injected on a
25 m × 0.22 mm BPS (5% phenyl-methyl silicone) cap-
illary column using helium as a carrier gas with split
ratio 1:100 and interface temperature 230 ˚C. Data acqui-
sition and processing were performed by Jeol JMA DA
5000 system. Various components were identified by
their retention time and peak enhancement with standard
samples and MS library search.
3. Result and Discussion
The aim of present studies was to investigate composi-
tion of essential oil of Zanthoxylum ar m atum by GC-MS.
3.1. Composition of Essential Oil
Examination of essential oil o f Zanthoxylum armatum by
GC-MS revealed the presence of twenty-two components.
Percentage of unidentified and identified fraction of oil
was 34.554% and 68.364%. Table 1 shows the list of
compounds identified by GC-MS, and mass data of the
components of essential oil of Zanthoxylum armatum.
GC-MS results showed that 3-borneol (9.718%), iso-
bornylacetate (9.574%) and dihydro carveol (8.816%)
are the components of highest percentage in the essen tial
oil of Zanthoxylum armatum.In general citrus are mostly
studied species of family Rutaceae [22,23] reported hy-
drocarbon as a major fraction of Essential oil of Sweet
orange, lemon and grapefruit ranging from 83% - 95%
and oxygenated components of these oils reported are in
the range of 1.64% - 1.5%.
3.2. Comparison of Oil
The oxygenated components contribute to the flavor of
oil. The alcohol, aldehyde and ether may contribute to
the aroma of extracted oil [24]. In present studies, major
fraction of the essential oil of Zanthoxylum armatum is
oxygenated i.e. 39.21%, which is very far enough by the
reported value, generally falls in the range of 1.6% -
3.0% [25,26]. Percentage of monoterpene hydrocarbons
calculated from GC-MS (Nist library) results was
(10.093%), oxygenated monoterpenes (37.238%), ses-
quiterpenes hy- drocarbon (7.265%) and oxygenated
sesquiterpenes (3.571%) respectively. Decanal, octanal
and nonal are the most commonly observing aldehydes
in sweet orange and other species of citrus [19,27,28]
reported aldehydic content of essential oil of sweet or-
ange as octanal (0.2% - 2.8%) and decanal (0.1% -
Table 1. Percentage Composition Of zanthxylum armatum
Essential Oil.
Component Percentage
 -pinene 0.685
 -terpinene 0.516
Sabinene 2.329
3-carene 0.698
 -pinene 1.889
 -phellendrene 0.661
terpinolene 2.148
 -terpinene 1.167
dihydro carveol 8.816
3-borneol 9.718
iso thujanol 3.596
terpinen-1-ol 0.697
iso pulegol 1.48
sabinene hydrate 0.903
iso fenchol 2.454
isobornyl acetate 9.574
trans-caryophyllene 3.074
humelene oxide 0.497
 -elemene 4.191
caryophyllene oxide 0.497
hexadecanoic acid 6.186
15-hexadecanolide 6.588
0.7%). The aldehydic content of Zanthoxylum armatum
analysed by GC-MS in present studies was much higher
i.e. 6.588% than found in other species of Rutaceae fam-
ily 16-hexadecanoloide was the only cyclic ester was
found in the essential oil of Zanthoxylum armatum.
Major portion of oxygenated fraction of the oil was
comprised by alcohols i.e. 26.761%. dihydro carveol,
3-borneol, iso-thujanol, terpinene-1-ol, iso-pulegol, and
iso-fenchol were the alcohols which were observed in
predominant percentages in the essential oil of Zan-
thoxylum arm a t um (Table 2).
Alcohols in oil are believed most important to flavor.
It is also used as flavoring agents in the confectionery
industry and in the manufacture of soft drinks, pharma-
ceutical and perfumery industries [29,30].due to the
presence of oxygenated components the oil is recom-
mended for flavoring agents in beverages and food

A. WAHEED ET AL. 260
Table 2. Mass Data of Essential Oil of Zanthoxylum arme-
tum by GC-MS.
Component Mass data
 -pinene (M+, 25), 136 (25%), 121 (8%), 105
(9%), 93 (100%), 41 (10%)
 -terpinene (M+, 20), 121 (17%), 105 (12%), 93
(100%), 77(35%), 65 (10%), 51 (10%)
Sabinene (M+, 55), 121 (17%), 105 (10%), 93
(100%), 77 (12%) 51 (5%), 41(45%)
3-carene (M+, 22), 121 (20%), 93 (100%), 77
(25%), 51 (7%) , 41 (27%)
 -pinene (M+, 10), 121 (12%), 105 (10%), 93
(100%), 79 (13%), 69 (35%), 53 (7%),
41 (25%)
 -phellendrene (M+, 45), 121 (3%), 105 ( 5%), 93
(100%), 91 (95%), 77 (45%), 65
(12%), 51 (10%), 41 (10%)
terpinolene (M+, 70), 121 (89%), 105 (35%), 93
(100%), 79 (55%), 67 (20%), 51
(28%), 41 (45%)
 -terpinene (M+, 48), 121 (100%), 105, (35%), 93
(72%), 77 (30%), 65 (5%), 41 (29%)
dihydro carveol (M+, 1%), 136 (50%), 81 (70%), 107
(45%), 93 (48%), 79 (25%), 67 (40%),
55 (20%), 41 (100%)
3-borneol (M+, 5), 137 (7%), 121 (17%), 95
(100%), 91 (25%), 81 (28%), 41 (15%)
iso thujanol M+, 136 (2%), 121 (25%), 95 (50%), 79 (45%), 67 (48%) , 55 (50%), 43
(100%)
terpinen-1-ol M+, 136 (40%), 137 (51%), 121 (48%), 93 (55%), 81 (98%), 67 (30%), 55
(50%), 43 (100%)
iso pulegol (M+, 2), 121 (40%), 11 (7%), 95 (48%), 81 (55%), 67 (78%), 55 (50%), 41
(100%)
sabinene hydrate (M+, 2), 139 (7%), 121 (15%), 111 (18%), 93 (20%), 81 (22%), 71 (40%),
55 (30%), 43 (100%)
iso fenchol (M+, 1), 136 (10%), 121 (5%), 111
(8%), 81 (100%), 67 40%), 43 (45%)
isobornyl acetate M+, 154 (5%), 136 (40%), 121 (45%), 108 (9%), 95 (75%), 81 (20%), 67
(22%), 55 (15%), 43 (100%)
trans-caryophyllene (M+, 3), 189 (7%), 175 (4%), 161 (9%), 147 (15%), 133 (40%), 105 (45%), 91
(60%), 79 (48%), 69 (40%), 41 (100%)
humelene oxide (M+, 5), 161(3%), 138 (50%), 109 (55%), 96 (60%), 81 (40%), 67
(100%), 43 (85%)
 -elemene
(M+, 2), 189 (5%), 175 (3%), 161
(20%), 133 (17%), 121 (22%), 105
(50%), 93 (70%), 79 (80%), 67
(100%), 41 (72%)
caryophyllene oxide M+, 187 (6%), 161 (8%), 149 (9%), 121 (25%), 107 (30%), 91 (60%), 79
(72%), 67 (45%), 41 (100%)
hexadecanoic acid (M+, 45), 239 (55%), 213 (45%), 185 (48%), 157 (46%), 129 (59%), 60
(100%), 41 (98%)
15-hexadecanolide (M+, 10), 236 (42%), 218 (20%), 192
(13%), 55 (100%), 39 (80%)
products. In the preparation of certain traditional dishes
the use of timur as a flavoring agent or spice is very pop-
ular [17]. Alcoholic compounds found in Zanthoxylum
armatum are variab ly found in the essential oils of sweet
orange, lemon and grape fruit, but in low concentration
as compared to the present studies. -terpineol and ter-
pinene-4-ol are known as degradation products of limo-
nene in citrus essential oils [31].
4. Conclusions
In previous studies [12,14] limonene is present in Zan-
thoxylum armatum but in our study no limonene was
found in the essential oil of Zanthoxylum armatum. The
prominent monoterpene hydrocarbons are -pinene
(0.685%), sabinene (2.329%) and  -terpinolene (2.148%).
[19,20] reported myricene,  -pinene and sabinene the
monoterpene hydrocarbon with second highest percent-
age after limonene. Only two compounds identified as
sesequiterpene i.e. trans-caryophyllene and  -elemene
with 3.074% and 4.191% respectively.
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