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Volatile Flavor Components of

Watermelon (Citrullus vulgaris)
a a a a
Izumi Yajima , Hidemasa Sakakibara , Junichi Ide , Tetsuya Yanai
a
& Hayashi Kazuo
a
Kawasaki Research Laboratories, T. Hasegawa Co., Ltd., 335
Kariyado, Nakahara-ku, Kawasaki 211, Japan
Published online: 09 Sep 2014.

To cite this article: Izumi Yajima, Hidemasa Sakakibara, Junichi Ide, Tetsuya Yanai & Hayashi Kazuo
(1985) Volatile Flavor Components of Watermelon (Citrullus vulgaris), Agricultural and Biological
Chemistry, 49:11, 3145-3150

To link to this article: http://dx.doi.org/10.1080/00021369.1985.10867246

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 Agric. Bio!. Chern., 49(11),3145",3150,1985 3145

Volatile Flavor Components of Watermelon (Citrullus vulgaris)

Izumi "'YAJIMA, Hidemasa SAKAKIBARA, Junichi IDE,

Tetsuya YANAI and Kazuo HAYASHI
Kawasaki Research Laboratories, T. Hasegawa Co., Ltd.,
335 Kariyado, Nakahara-ku, Kawasaki 211, Japan
Received March 14, 1985

Volatile flavor components of watermelon fruit (Citrullus vulgaris) were obtained by distilling
juice under reduced pressure and extracting the resulting distillate with Freon-II. The volatiles were
separated into acidic and neutral fractions and then analyzed by gas chromatography and gas
Downloaded by [University of Arizona] at 23:27 17 December 2014

chromatography-mass spectrometry.
Fifty-two compounds were found for the first time as flavor components of watermelon.
Among them, the following compounds have not been previously reported as naturally occurring
fl'lvor components: 4-oxononanal and 2-hydroxy-, 2-pentyloxy-, 2-hexyloxy-, 2-octyloxy-, 2-
nonyloxy-, 2-[(Z)-3-noneyloxy]-, 2-[(Z)-2-nonenyloxy]-, 2-[(Z,Z)-3,6-nonadienyloxy]-, 2-benzyl-
oxy-, and 2-phenetyloxy-5-pentyltetrahydrofurans.

There have been a limited number of reports Methods.

concerning volatile flavor compounds of
watermelon (Citrullus vulgaris), although
many investigations of the volatile constitu-
ents of closely related fruits such as melon and
cucumber have been published.
Katayama and Kaneko!) studied water-
melon volatiles, identifying 26 compounds by
gas chromatography. Kemp et al?) isolated
(Z,Z)-3,6-nonadien-l-ol from watermelon
flesh and described its odor as reminiscent of
watermelon or watermelon rind. K emp 3) iden-
tified 18 compounds including 10 aliphatic C g
alcohols and aldehydes from watermelon es-
sence. However, the combination of these
compounds was found to be insufficient to
reconstruct the fine aroma of watermelon.
This investigation was undertaken to iden-
tify any additional compounds contributing to
the characteristic aroma of watermelon.
MATERIALS AND METHODS
Materials. Watermelon fruits harvested in Ibaraki
Prefecture were used. Two hundred and one kilograms of
flesh were obtained by removing rinds and seeds from
438 kg of the fresh fruits. The physical properties of the
flesh were as follows: Brix, 8.4; pH, 5.5; acid value, 0.74.
1) Collection and fractionation of volatile flavor com-
pounds. Two hundred kilograms of the flesh were pressed,
and the resulting juice was immediately mixed with 70 kg
of McIlvaine buffer solution (pH 6.6) to prevent the
development of an off-flavor. The mixture was distilled
under reduced pressure (28°C and 10 mm Hg) and 70 kg of
the distillate was extracted with 21 liters of Freon-II.
The extract, after drying over Na2 S04 , was concen-
trated to give a flavor concentrate with a strong pleasant
odor of watermelon.
The flavor concentrate was separated into acidic and
neutral fractions by the usual method. After concentrating
to about 0.2 ml, the neutral fraction was further separated
into 10 fractions by column chromatography, using a
17 mm i.d. x 240 mm column packed with silica gel
(Wacogel C-200) and the following solvent systems (v/v,
60 ml each): pentane, pentane-ethyl ether (99 : I), pentane-
ethyl ether (97: 3), pentane-ethyl ether (95: 5), pentane-
ethyl ether (90: 10), pentane-ethyl ether (70 : 30), pentane-
ethyl ether (50: 50), pentane-ethyl ether (30: 70), ethyl
ether and methanol. Each fraction was concentrated to
about 0.2ml.
2) Identification of the volatiles. All fractions were
analyzed by gas chromatography (GC) and gas
chromatography-mass spectrometry (GC-MS), with the
exception of the acidic fraction which was analyzed after
methylation.
Identification was made by comparing and matching the
mass spectra and GC· retention times of the unknown
compounds with those of authentic compounds. One of
the unknown compounds was isolated by preparative GC
and then analyzed by GC, GC-MS and infrared (IR)
 3146 I. Y AJIMA et al.
spectrometry.
a) GC and GC-MS. GC was done using a Hitachi Model
163 gas chromatograph with a flame ionization detector
(FID) and a 0.28mm i.d. x 50m glass SCOT column
coated with PEG 20 M. The temperature was programmed
from 70 to 190°C at 2°C/min and the flow rate of the
nitrogen carrier gas was 1ml/min.
GC-MS was done on a glass SCOT column (0.28 mm
i.d. x 50m) coupled to a Hitachi Model RMU-6MG mass
spectrometer. The column temperature was programmed
from 60 to 200°C at 2°C/min. The operating conditions for
mass scans were: ionization voltage, 70eV; accelerating
voltage, 3200 V; ion source temperature, 200°C.
b) IR spectrometry. The IR spectrum was recorded on a
JASCO IRA-2 spectrometer, using an ultra-micro cavacity
Downloaded by [University of Arizona] at 23:27 17 December 2014
cell (2 fll) and a reflecting beam condenser.
3) Preparative GC. Preparative GC was done using a
Hitachi Model 163 gas chromatograph with an effluent
splitter and a 3 mm i.d. x 4 m glass column packed with
10% PEG 20 M on Celite 545 SK80j100. The effluent was
proportioned by the splitter at a ratio of 1 to 100, the first
portion being passed to an FID circuit and the second to
the exit port which was attached to a Teflon tube cooled by
dry ice, according to the procedure of Teranishi et al. 4 ) The
column temperature was programmed from 70 to 190°C at
2°C/min with the nitrogen carrier gas at a flow rate of
20ml/min.
4) Sniffing evaluation of the flavor compounds emitted at
each peak on the gas chromatograms. A sensory evaluation
was accomplished by sniffing at the exit port of a Hitachi
Model 163 gas chromatograph fitted with ail effluent'
splitter, while the samples were being eluted. The effluent
was proportioned by the splitter at a ratio of 1 to 10, the
first portion being passed to an FID circuit and the second
to the exit port which was heated to 180°C by a small
heater to prevent condensation. A 0.5 mm i.d. x 70 m glass
SCOT column coated with PEG 20 M was used. The other
operating conditions were the same as those for the GC
conditions.
5) Syntheses of authentic compounds. 4-0xononanal and
2-hydroxy, 2-ethoxy-, 2-pentyloxy-, 2-hexyloxy-, 2-oc-
67 69
70
27 39
FIG. 1. Gas Chromatogram of the Flavor Concentrate form Watermelon.
tyloxy-, 2-nonyloxy-, 2-[(Z)-3-nonenyloxy]-, 2-[(Z)-2-non-
enyloxy]-, 2-[(Z,Z)-3,6-nonadienyloxy]-, 2-benzyloxy-,
and 2-phenethyloxy-5-pentyltetrahydrofurans were syn-
thesized by the procedures of Iwamoto et al. 5 )
RESULTS AND DISCUSSION
In a preliminary experiment concerning the
effects of pH on the flavor stability of fresh
watermelon juice, it was found that the juice at
pH 5.6 developed an off-flavor when allowed
to stand. Such a flavor change was observed
when adjusting the pH of the juice to 5.0, 4.5,
4.0, 3.5, and 3.0, or adding NaCl to the juice.
On the other hand, the flavor of the juice was
relatively stabilized by adjusting the pH of the
juice between 6.0 and 7.0.
In this study, therefore, the flavor change
during the collection period of the volatiles
was minimized by adjusting the pH of the juice
to about 6.6.
The approximate yield of the total flavor
compounds was 350 mg, which was equivalent
to about 1.7 ppm of the weight of the water-
melon flesh.
Figure 1 shows a gas chromatogram of the
flavor concentrate from the watermelon juice.
The two most· abundant components in the
flavor concentrate were found to be (Z)-3-
nonen-I-ol (Peak 69) and (Z,Z)-3,6-nonadien-
1-01 (Peak 74) in agreement with results pre-
viously reported by Kemp?) A gas chromato-
gram pattern of the neutral fraction was al-
most the same as that of the flavor concen-
trate, whereas the acidic fraction showed ·no
74 83
94
81
110
7 . (Min)
 Volatile Flavor Components of Watermelon
TABLE I. ODOR CHARACTERIST~CS OF THE FRACTIONS OBTAINED FROM THE NEUTRAL FRACTION
Wt% of the neutral
Fraction No.
fraction
Original neutral
100
fraction
Sub-fraction 1 1 Hydrocarbon-like
2 1
3 15
4 4
5 22
6 52
7 3
8 1
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9 1
10 Trace
peak in a chromatogram because of its
trace quantities.
Table I lists the odor characteristics of the
fractions which were obtained from the neutral
fraction by column chromatography. Frac-
tions 3, 5, and 6, which together amounted
to 90% of the neutral fraction, were consid-
ered to be essential to the aroma of water-
melon judging from their odors.
As a result of an odor evaluation of the
individual compounds in Fractions 3, 5, and 6
at the exit port of the gas chromatograph, (Z)-
3-nonenal (Peak 49), (Z,Z)-3,6-nonadienal
(Peak 58), (Z)-3-nonen-I-ol, (Z,Z)-3,6-
nonadien-I-ol and the two unknown com-
pounds corresponding to Peak 81 and Peak 83
were considered to be important to the aroma
of watermelon. In Fraction 3, both (Z)-3-
nonenal and (Z,Z)-3,6-nonadienal had green
and somewhat watermelon-like odors. (Z)-3-
Nonen-I-ol found inFractions 5 and 6 in large
quantities had a pleasant and somewhat fresh
melon-like odor. (Z,Z)-3,6-Nonadien-1-01 was
also found in Fractions 5 and 6, and the odor
of this compound was sweet and watermelon-
like. This compound was thought to be the,
most powerful contributor to the characteristic
aroma of watermelon judging from its odor
characteristic. (Z)-3-nonenal and {Z,Z)-3,6-'
nonadienal have been tentatively identified
from cucumber essence by Kemp et al. 6 ) They
have reported that the odor of the former
3147
Odors
Sweet, pleasant, watermelon-like
Spicy, vegetable-like
Green, somewhat sweet
Green, somewhat oily
Fresh fruit-like, somewhat green, fresh melon-like
Sweet, watermelon-like, somewhat green
Sweet, lactone-like
Sweet
Faintly sweet
Very weak
compound was somewhat reminiscent of that
of cucumber whereas that of the latter com-
pound was reminiscent of that of watermelon
as they were eluted from the gas chromato-
graph. (Z,Z)-3,6-Nonadien-1-01, known to
possess an odor reminiscent of that of water-
melon or watermelon rind, has been found in
watermelon,2) muskmelon,2) and cucumber. 6)
Both Peak 81 and Peak 83 found in Fraction
6 had pleasant, fruity and somewhat green
odors, and they were thought to contribute to
the fresh note in the aroma of watermelon.
Peak 81 was isolated by preparative GC and
then used for spectral analyses.
Figures 2 and 3 show the IR and mass
spectra of this compound. The IR spectrum
indicates that this compound is probably an
aliphatic saturated aldehyde. Its molecular
weight is 156 according to the mass spectrum,
suggesting the formula of C 10 H 20 0 or
C 9 H 16 0 2. From the IR and mass spectral data
this compound is supposed to be a carbonyl
compound having no branched-chain. The
mass peak at m/z 100 may be due to CH 2 ==
+ +
C(OH)CH 2CH 2CHO or CH 2 ==C(OH)C4 H g
. yielded from the'molecular ion by McLafferty
rearrangement. On the other hand, the peaks
at m/z 99 and 85 suggest that the ketone oxy-
gen is located on C4 . These observations led
to the conclusion that this compound is 4-
oxononanal. Further confirmation was made
 3148 1. Y AJIMA et al.

by comparing the mass and IR spectra of this
compound with those of 4-oxononanal syn-
thesized in our laboratory. Although 4-oxo-
nonanal has been reported as a possible pre-
cursor of 2-pentylfuran,7) this aldehyde has
not been previously reported as a naturally
occurring flavor constituent.
Peak 83 gave the following mass spectral
data: m/z(%), 140(M+ -H 2 0, 7), 87 (100), 82
Downloaded by [University of Arizona] at 23:27 17 December 2014
(25), 70 (22), 69 (50), 58 (24), 57 (26), 55 (57),
43 (50), 40 (61). From these data this com-
pound was considered to be 4-hydroxynonanal
or 2-hydroxy-5-pentyltetrahydrofuran. These
two compounds were synthesized and their
GC retention times and mass spectral data
were compared with those of Peak 83. Thus,
this compound was assigned as 2-hydroxy-
5-pentyltetrahydrofuran.
Furthermore, several compounds giving
similar mass fragment patterns to those of 2-
100

-~
2 80 43

-E 60 85
1410 71
2925
~p::; 40 72
99
58
1710 20 100

I
128
113
I 138 156 (M+)
11 I
20 40 60 80 100 120 140 160
4000 2000 1500 _11000 500
WAVELENGTH em m/z

FIG. 2. IR Spectrum of Peak 81. FIG. 3. Mass Spectrum of Peak 81.

TABLE II. MASS SPECTRAL DATA OF 5-PENTYLTETRAHYDROFURAN DERIVATIVES

~OR
Peak No. -R m/z (%)

49 a -C2H s 186(M, 1), 141(15), 123(17), 115(24),

87(100), 69(60), 55(52)
70 a -CSH ll 228(M,0.5), 157(67), 141(57), 123(20),
87(100), 81(39), 71(57), 55(54), 43(88),
41(55)
78 -C6 H 13 171(38), 141(47), 123(18), 87(54), 85(33),
55(33), 43(100), 41(46), 29(33)
93 -CS H 17 199(56), 141(100), 123(41),87(94),81(35),
71(82), 57(88), 55(74), 43(91), 41(62)
98 a -C9 H 19 213(41), 141(75), 123(33),87(100),
71(45), 57(55), 55(50), 43(70), 41(40)
101 -CH2~ 211(3),157(5),141(100),123(45),83(15),
81 (40), 79(33), 77(27), 55(38), 41 (30)
102 -CH2~ 238(0.5), 157(8), 141(59), 123(53), 87(38),
83(53), 81(73), 69(100), 67(50), 57(59)
103 -CH2~ 209(3), 141(58), 123(34),81(76),67(66),
55(68), 41(100)
106 -CH2 {J) 248(M,2), 177(4), 157(10), 141(11), 123(9),
109(9), 92(16), 91(100), 81(10)
110a -CH 2CH 2 -Q 262(M,0.5), 191(6), 184(3), 157(22), 141(70),
123(40), 105(100), 104(52),81(50),67(35),55(38)

a
Overlapping peaks.
 Volatile Flavor Components of Watermelon 3149

T ABLE III. VOLATILE FLAVOR COMPOUNDS IDENTIFIED FROM WATERMELON

Peak No. Compounds Peak No. Compounds

Hydrocarbons 49 a (Z)-3-Nonena1
55 Pentadecane 51 (E, Z)- 2,4-Heptadienal
58 Pentadecene-1 55 a (E,E)- 2,4-Heptadienal
63 Hexadecane 56 Benzaldehyde
70 Heptadecane 58 a (Z,Z)-3,6-Nonadienal
63 a ,b (E,Z)-2,6- N onadienal
79 Octadecane
86 Nonadecane 68 Neral
98 Heneicosane 73 b Geranial
Alcohols 76 (E,Z)-2,4- Decadienal
3 b
Ethanol 79 a (E,E)- 2,4-Decadienal
16 b I-Butanol 81 4-0xononanat
Downloaded by [University of Arizona] at 23:27 17 December 2014

19 1-Penten-3-o1 Ketones
22 3-Methylbutanol 21 2-Heptanone
27 b
1-Pentanol 36 1-0cten-3-one
34 (Z)-2-Penten.-1-o1 37 a 6-Methyl-5-hepten-2-one
39 b
1-Hexanol 43 2-Nonanone
40 (E)-3-Hexen-1-o1 67 a Acetophenone
42 b
(Z)-3-Hexen-1-o1 82 Geranyl acetone
49 1-0cten-3-o1 88 b [3-Ionone
60 1-0ctanol 91 a [3-Ionone epoxide
64 (E)-2-0cten-1-o1 110 Farnesyl acetone
67 b
1-Nonanol Lactones
69 b (Z)-3- N onen-1-o1 64 a 4-Butanolide
70 a ,b (Z)-6-Nonen-1-o1 94 4-N onanolide
74 b (Z,Z)-3,6-Nonadien-1-o1 Furans
75 b (E,Z)-2,6- N onadien-1-o1 27 a 2-Pentylfuran
83 a Geraniol 49 a 2-Ethoxy-5-pentyltetrahydrofuran
83 a ,b Benzyl alcohol 70 a 2-Pentyloxy-5-pentyltetrahydrofuran
86 a Phenethyl alcohol 78 2-Hexyloxy-5-pentyltetrahydrofuran
91 Dodecanol 83 2-Hydroxy-5-pentyltetrahydrofuran
104 Cinnamyl alcohol 93 2-0ctyloxy-5-pentyltetrahydrofuran
Aldehydes 98 a 2-Nonyloxy-5-pentyltetrahydrofuran
7 Pentanal 101 2-[(Z)-3-Nonenyloxy]-5-pentyl
14b Hexanal tetrahydrofuran
17 (E)-2-Pentenal 102 2-[(Z)-2-Nonenyloxy]-5-pentyl-
26 b
(E)- 2-Hexenal tetrahydrofuran
32 Octanal 103 2-[(Z,Z)-3,6- N onadienyloxy]-5-
37 b
(E)-2- Heptenal pentyltetrahydrofuran
44 b Nonanal 106 2-Benzyloxy-5-pentyltetrahydrofuran
48 b (E)- 2-0ctenal 110a 2..Phenetyloxy-5-pentyltetrahydrofuran

a Overlapping peaks.
b Previously identified.

hydroxy-5-pentyltetrahydrofuran were found oxy]-, 2-benzyloxy-, and 2-phenethyloxy-5-

in Fractions 5 and 6 as minor constituents.
Their mass spectral data are listed in Table II.
By comparing these data with those of au-
thentic compounds synthesized in our labo-
ratory, these compounds were identified as 2-
ethoxy-, 2-pentyloxy-, 2-hexyloxy-, 2-octyl-
oxy-, 2-nonyloxy-, 2-[(Z)-3-nonenyloxy]-, 2-
[(Z)-2-nonenyloxy]-, 2-[(Z,Z)-3,6-nonadienyl-
pentyltetrahydrofurans, respectively. To our
knowledge, these compounds including 2-
hydroxy-5-pentyltetrahydrofuran have not
been reported previously as naturally occur-
ring flavor constituents.
Table III lists the compounds identified
from the watermelon juice. Among them, 52
compounds were found for the first time as
 3150 I. Y AJIMA et al.
flavor components of watermelon. No acids
and esters could be found in this study, al-
though 11 ester compounds have been" iden-
tified from watermelon by Katayama and
Kaneko. l )
As can be seen "from Table III, 10 aliphatic
Cg alcohols and aldehydes, including 4-oxo-
nonanal, were found in the juice. These com-'
pounds were thought to be important to the
aroma of watermelon. With regard to biosyn-
thesis of C g aldehydes, Grosch and Schwarz8 )
have shown that (E)-2-nonenal and (E,Z)-2,6-
Downloaded by [University of Arizona] at 23:27 17 December 2014
nonadienal were related to linoleic and lino-
lenic acid, respectively. Tressel and Drawertg )
have reported that (E,Z)-2,6-nonadienal may
possibly be biosynthesized via 9-hydroperoxy
acid from linolenic acid in unripe bananas.
Hatanaka et al. lO ) have also shown a biosyn-
thetic pathway for the development of (Z,Z)-
3,6- and (E,Z)-2,6-nonadienals and the cor-
responding alcohols in cucumber. They have
proposed that (Z,Z)-3,6-nonadienal was pro-
duced through the oxidative splitting of lino-
lenic acid and subsequently isomerized to
(E,Z)-2,6-nonadienal. They have also reported
that these aldehydes were. further hydrogen-
ated to the corresponding alcohols by alcohol
dehydrogenase. Kemp et al. 2 ) have mention-
~d possible C l8 fatty acid" precursors of ali-
phatic C g aldehydes and alcohols isolated
from muskmelon essence. These investiga-
tions suggest that the Cg aldehydes and
alcohols identified from" watermelon juice
have also been formed enzymatically from
unsaturated C l8 fatty acids. However, it is
uncertain whether 4-oxononanal .has been
produced through enzymatic oxidation. Chang
et al. 7 ) isolated and identified 2-pentylfuran as
contributing to the reversion flavor of soy-
bean oil, and they have shown a possible
mechanism for the formation of 2-pentyl-
furan via 4-oxononanal from linoleic acid
by autoxidation. Further detailed experi-
ments are necessary to show a possible path-
way for the formation of 4-oxononanal in
watermelons.
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1) O. Katayama and K. Kaneko, Nippon Shokuhin
Kogyo Gakkaishi, 16, 474 (1969).
2) T. R. Kemp, D. E. Knavel, L. P. Stoltz and R. E.
Lundin, Phytochemistry, 13, 1167 (1974).
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4) R. Teranishi; R. A. Flath, T. R. Mon and K. L.
Stevens, J. Gas Chromatogr., 3, 206 (1965).
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7) S. S. Chang, T. H. Smouse, R. G. Krishnamurthy, B.
D. Mookherjee and R. B. Reddy, Chem. Ind., 1926
(1966).
8) W. Grosch and J. M. Schwarz, Lipids, 6, 351 (1971).
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510 (1973).
10) A. Hatanaka, T. Kajiwara and T. Harada,
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