Studies on the Components of Essential Oil of <i>Zanthoxylum Armatum</i> by Gc-Ms

doi:10.4236/ajac.2011.22031

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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

E-mail: [email protected]

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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