1I.111I1~IIYllllmllllll.
EJ52-1984-93
COMPOSITION OF PEEL ESSENTIAL OILS FROM
EIGHT CITRUS SPECIES
YU-SHIA CHENG (.:E.~) and
IHpartmt1lt 01 Chemistry, NatlO1lQI Taiwan University,
Taipei. Taiwan 101
Key Word Index-eitrus; Essential Oils
The peel essential oils from eight citrus species growing in Taiwan were
analysed to determine the detailed composition of each oil.
Citrus peel oils are major by-product of
the Citrus processing industry. They are used
as flavoring ingredients in a variety of foods,
frozen desserts, confectionery, and also in
perfumery industry. Although much of the
chemistry of Citrus oil components have been
reported":", . the peel essential oils of Citrus
species growing in Taiwan have not been
studied very well. The present work is a
comparative chromatographic study using the
steam-distilled and cold-pressed peel oils,
EXPERIMENTAL
The peel of fresh fruit was steam distilled
in a stainless steel apparatus. The distillate
was extracted with hexane after being
saturated with sodium chloride. The percent-
age yields of the essential oils of these samples
are tabulated in Table I. The essential oils
were chromatographed on silica gel column.
Each isolated fraction was further fractionated
by preparative gas chromatography. The
components which isolated in sufficient amount
were identified by IR and NMR spectra and
retention time of OLC with those of authentic
samples. Identifications of the minor com-
ponents are based on retention time data and
peak enrichment techniques. Authentic sam-
ples of' individual compounds were either
obtained from commercial sources or isolated
previously from other essential oils at this
CHUN-TzBR CHou (JliJ:l!!Jl$)
Table I. The yield of essential oils
Yield (%)
Species
atm tanktln Hayatr 1.14
Citrw poonensi:r Tanak. 1.29
CitnlS tan1can Hayola lorm. hairl Hort 0.85
Citrw paradisl Mac/. 0.96
0.94
Citrus maxima (Bunn. f.) Merrill
CilnlS maxima (Burm. /.)
Merrill, form. blmtan (HQ)'Qta) Hort 1.01
Citt1J3 slntnsi:r Osbeck lorna 1.09
1.27
Citrw limon Burn
laboratory.
Quantitative OLe analyses were carried
out on a Hewlett-Packard model 5710A gas
chromatograph using flexible fused silica
capillary column (25 m XO.2 mm id) coated
with Carbowax 20 M. The column temperature
was programmed from 70·C to 200·C at the
rate of 4·C/min. Column was operated by
using nitrogen as carrier gas at the flow rate
of 0.5 mljmln. A Hewlett-Packard model 3380A
reporting integrator was used to determine
peak areas without correction for responsed
factors.
RESULTS AND DISCUSSION
The compositions of steam-distilled peel
oils of Citrus species is shown in Table II.
The cold-pressed peel oils were analyzed using
the same instrument. Retention time matching
has been done by using similar column. The
result is shown in Table III.
J. CJdM. Clrtm. Soc. 31, 93-96, 1984
94 Y.S. CItllNO AND C. T. CHOU

Table II. The compositions of steam-distilled peel oils of citrus species

Peak No. Compounds I{%) n (%) III (%) IV (%) V (%) VI (%) VII (%) vnr (%)

I. a-Pinene 0.4S 1.16 0.09 0.49 0.55 0.26 0.49 1.74

2. Camphene 0.01 0.05 0.09
3. ~-Pinene 2.45 0;01 0.06 9.30
4. Sabinene 0.07 0.44 0.25 2.88 0.19 0.36 1.30
S. A·.carene 0.09
6. ~-Myrcene 1.86 2.07 1.47 1.86 31.91 1.16 1.92 1.51
7. a-Terpinene 0.47
8. Limonene 95.45 89.15 94.21 93.33 55.84 94.16 93.44 68.51
9..p-Pbyllandrene 0.01 4.59 0.14 0.10 0.37 0.18 9.67
10. 1,S-eineole 0.08 0.11 0.01 0.10 1.38 0.28 0.05 0.29
II. ~-OCimene 0.29 0.01 0.04 . 0.08 0.74
12. r-Terpincnc 0.01 0.07 1.09 0.16 0.46 0.10
13. p-Cymcnc 0.01 0.07
14. Nonyl aldehyde 0.12 0.39 0.02 0.06 0.10
15. Citronellal 0.40 O.OS 0.01
16. Unidentified 0.13 0.29
17. Unidentified
18. Decyl aldehyde
19. Linalool 0.78 0.24 1.30 0.27 8.41 1.07 0.74 0.09
20. LiDalYCacetatc 0.01 0.20
21. Caryophyllcnc 0.08 0.24 0.10 0.09
22. 4-Terpineol 0.42 0.07 0.58 1.08
23. Citronellyl acetate 0.01 0.01 0.05
24. Neral 0.21 0.68 0.19 0.98
25. a-Terpineol 0.02 0.46 0.42 0.32 0.29 1.65
26. a-Terpinyl acetate 0.10 0.43 0.02 0.38
27. Neryl acetate 0.13 0.15 0.06 0.07
28. Oeranial 0.04 O.OJ 0.38 1.04 0.28 ),19
29. Geranyl acetate 0.08 0.03 0.01 0.08 0.06 0.02
30. Citronello} 0.02 O.OS 0.03 0.35
31. Nerol 0.01 0.01 0.55 0.14 0.27 0.35
32. Geraniol 0.04 0.02 e.n 0.J4 0.02 0.43
33. Thymol 0.24 0.23 0.08
(I) at,.., tanhm Hqata
(Il) Cihvl pomrensls TQIIQk.
(Ill) Cit,.., ttmkan Bayata fonn. hairl Hart
(IV) Cit1'tl3 porod/d Mac!.
(V) Citl1lJ max/11J4 (Burm. f.) Merrill
(VI) CitNU maxi11J4 (Bllrm./.) Merrill, form. buntan (Hayato) Hart
(VII) Citl'1l8 81~nsh OslJeck IOT7IQ
(VITI) Citl'U3 limon Burn
 COMPOSITION OF PI!J!L EssENTIAL OILS FROM EIGHT CITRUS SPECIES 9S

Table III. The compositions of cold-pressed peel oils of citrus species

Peak No. Compound 1(%) II (%) III eo IV (%) V (%) VI (%) VII (%) VIn (%)

1. a-Pinene 0.53 0.92 0.Z1 0.57 0.31 0.46 0.64 1.71

2. Camphene 0.16 O.OS
3. p-Pinene 0.20 0.22 0.08 1.34 9.47
4. Sabinenc 0.13 0.30 0.30 0.72 0.19
S. lo'-carene
6. IJ-Myrcene 1.15 0.84 1.67 2.07 28.03 1.94 1.71 1.77
7. a-Terpinene
8. Limonene 96.53 86.47 92.92 94.99 69.55 95.85 94.74 72.80
9. Jl-Phyllandrene 0.06 3.56 0.12 0.07 0.04 8.41
10. 1,8-Cineole 0.08 0.07 0.11 0.02 0.37
11. Jl...()clmene 0.93 0.16 0.04 0.03
12. r-Terpinene 0.19 0.52 0.14
13. p-Cymene 0.50
14. Nonyl aldehyde 0.03 0.06
15. Citronellal 0.10 0.52 0.24 0.03 0.05 0.14 0.03
16. Unidentified
17. Unidentified 0.08
18. Decyl aldehyde 0.08 0.03 0.08
19. Linalool 0.65 3.84 1.21 0.11 0.25 0.07 0.34 0.21
20. Linalyl acerate 0.32 0.03 0.02 0.17
21. Caryophyllene 0.08 0.16 0.19
22. 4-Terpineol 0.02
23. Citronellyl acetate 0.03 0.91 0.04 0.02
24. Neral 0.05 0.09 1.11
25. It-Terpineol 0.02 0.63 0.01 0.06 0.02 0.06 0.29
26. a-Terpinyl acetate 0.03 0.07 0.72 0.12
Z7. Neryl acetate 0.30 0.51 0.08 0.28
28. Geranial 0.03 0.04 0.07 0.14 0.06 0.14 1.69
29. Geranyl acetate 0.10 0.16 0.29 0.05 0.11 0.06 0.47
30. Citronellol 0.02 0.07 0.01 0.29
31. Nerol 0.01 0.09 0.10 0.02 0.05
32. Geraniol 0.03 0.02 0.06
33. Thymol 0.02 0.02 0.06
(I) Cilnu lan1cIln Hayata
(II) Cilnu IJOO1"nsU Tanak.
(JII) Citnll tonkan Hayala form. hoM Hort
(IV) atnu JXlTadl# Mac/.
(V) Citnu maxima (Bunn. /.) Merrill
(VI) Citru.r maxima (Burm. f.) Me"llI, form. lmntan (Hayato) Hem
(VII) Cllnu slnenm Osbeck f017la
(Vm) Clmu l1mt)n .(Jum
96 Y. S. CHENG AND C.
Thirty-three compounds identified from
the analysis of whole essential oils are listed
in Table II and III in order of their GLC
retention times. From the data, it is clear
that the terpene hydrocarbons constitute the
highest proportion of the total makeup of the
investigated peel oils.
Limonene normally accounted for the
largest content of any constituent of citrus
oils being present in higher concentration in
the cold pressed than in the steam-distilled
peel oils. The limo,nene content of the steam-
distilled oil of Citrus maxima (Burm. f.)
Merrill (55.94%) is exceptionally lower than
that of the cold-pressed oil (69.55%). The
second major component of Citrus maxima
(Burm. f.) Merrill is ~-myrcene which ac-
counted for about 31.91% of the steam distilled
peel oil. This relatively high p-myrcene
content seems to bo a characteristic of peel
oil from Citrus maxima (Burm. f.) Merrtll, (3-
T. CHOU
phyllandrene was present in large amounts
only in Citrus poonensls Tanak,
Aeknowledgement: We are grateful to
Chemical Research Center, National Science
Council of China, for the financial support.
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( 4) G. F. Gostecnik, A. Zlatkis, J. Chromatogr.,
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(Received May 17,1983)