The synthesis and evaluation of vanillin derivatives as the fruit fly attractant

Article abstract of DOI:10.13005/ojc/3404063

The present study was conducted to synthesize 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone, a compound with similar structure to cue lure [4-(4-Acetyoxyphenyl)-2-butanone], using vanillin as a started material. The synthesis process was completed in two steps. The first step was the condensation reaction of Claisen Smidth between vanillin and acetone on alkaline conditions to produce 4-(4-hydroxyphenyl-3-methoxy)-3-buten-2-one, and the second step was the hydration reaction using zeolite catalysts activated by HCl, to produce 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone. Characterization of the compounds was performed using IR and ¹H-NMR spectroscopy. The evaluation of 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone as fruit flies’ attractant was carried out in yard areas planted with guava and start fruit, in the Klidon village, Sukoharjo, Sleman Yogyakarta, with methyl eugenol as a standard. The observations were made for 24 hours. The synthesis product was obtained in the form of a white-orange solid with a melting point of 79-81oC and 60% yield.The field test showed that 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone was potential as fruit flies’ attractant, indicated by the presence of lured fruit flies around the test location.

Full text of DOI:10.13005/ojc/3404063

ISSN: 0970-020 X
CODEN: OJCHEG
018, Vol. 34, No.(4):
Pg. 2197-2202
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
The Synthesis and Evaluation of Vanillin derivatives as the
Fruit Fly Attractant
1
1
1
SUSYYUNITA PRAbAwATI *, DAMAYANTI ISkANDAR and LIIMROATI PURwO SUCI
1
Department of Chemistry, Faculty of Science and Technology, Universitas Islam Negeri Sunan Kalijaga
Jl. Marsda Adisucipto, Yogyakarta 55281 Indonesia.
*
Corresponding author E-mail: susyprabawati@gmail.com
http://dx.doi.org/10.13005/ojc/3404063
(Received: June 08, 2018; Accepted: July 20, 2018)
AbSTRACT
The present study was conducted to synthesize 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-
-butanone, a compound with similar structure to cue lure [4-(4-Acetyoxyphenyl)-2-butanone], using
2
vanillin as a started material.The synthesis process was completed in two steps.The first step was
the condensation reaction of Claisen Smidth between vanillin and acetone on alkaline conditions
to produce 4-(4-hydroxyphenyl-3-methoxy)-3-buten-2-one, and the second step was the hydration
reaction using zeolite catalysts activated by HCl, to produce 4-(4-hydroxyphenyl-3-methoxy)-
1
4
-hydroxy-2-butanone. Characterization of the compounds was performed using IR and H-NMR
spectroscopy.The evaluation of 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone as fruit flies’
attractant was carried out in yard areas planted with guava and start fruit, in the Klidon village,
Sukoharjo, Sleman Yogyakarta, with methyl eugenol as a standard. The observations were made
for 24 hours. The synthesis product was obtained in the form of a white-orange solid with a melting
o
point of 79-81 C and 60% yield.The field test showed that 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-
2-butanone was potential as fruit flies’attractant, indicated by the presence of lured fruit flies around
the test location.
keyꢀords: 4-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-butanone, Attractant,
Cue lure, Canilin.
INTRODUCTION
Ithasbeenknownwidelythatusingpesticide
continuously will impose a serious negative impact
on the environment. In addition, consuming fruits
treated with pesticide may lead to the accumulation
of pesticide residues in body. One of the most easy
and efficient alternative solutions to control fruit flies
is using traps baited with attractant.
The post-harvest treatment of fruits to
control fruit flies attack usually involve the use
of synthetic pesticides. The most frequent and
damaging fruits flies for fruit harvest in Indonesia is
2
1
Bactrocera spp (Diptera: Tephritidae) .
This is an
.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/), which permits unrestricted
Non Commercial use, distribution and reproduction in any medium, provided the original work is properly cited.
Open Access article licensed under a Creative Commons Attribution-Non Commercial-Share Alike
4

PRABAꢀATI et al., Orient. J. Chem., Vol. 34(4), 2197-2202 (2018)
2198
Some attractant compounds that have
been studied, such as methyl eugenol (4-(4-Allyl-1.
2
-dimetoxybenzena), cue lure (4-(4-Asetoxyphenyl)-
-butanone) (Fig. 1a), and raspberry ketones
2
(
4-(4-Hydroxyphenyl)-2-butanone), are identified
as strong parapheromones to attract male fruit
flies. Those synthetic compounds have been
experimented with to monitor, detect and control fruit
3
flies. The results show that a total of 176 species
Fig. 1a.The structure of cue lure
of Dacinea male fruit flies are attracted to cue
lure/raspberry ketone, and 58 species are lured to
4
methyl eugenol.
However, a certain species of male fruit
flies is basically interested in specific attractant or
5
parapheromone. For example, the male melon fruit
fly (B.cucurbitae) is attracted to 4-(4-Hydroxyphenyl)-3-
butene-2-one, an intermediate compound of cue lure.
Apparently, with a considerable amount
of fruit fly species, the type of attractant or
parapheromone that is specifically attractive to
particular fruit fly species have not been completely
studied.Therefore, the continuing study of cue lure,
an analog of naturally occurring ketone raspberry is
required to control fruit flies.
Fig. 1ꢁ.The structure of 4-(4-hydroxyphenyl-3-methoxy)-4-
hydroxy-2-ꢁutanone
Vanillin is a compound containing aldehyde
groups that can undergo aldol condensation when
reacted with acetone in alkaline condition. The
reaction that occurs is shown in Figure 2.
The initial research conducted by Suci
et al., shows that the 4-(4-Hydroxyphenyl-3
6
In this study, a compound with similar
structure to vanillin cue lure, namely 4-(4-hydroxy phenyl-
-methoxy)-4-hydroxy-2-butanone (Fig. 1b), was
synthesized.
-methoxy)-3-buten-2-one is potential as an attractant
becauseitcancaptureonefruitflyonchili.Itseemsthat
the existence of a functional group-OH instrumental
in increasing its activities as an attractant.
3
Fig. 2.The aldol condensation of vanillin ꢀith acetone
To obtain the compound with similar
The materials used in this study consisted
of vanillin, NaOH, aquadest, acetone, ethanol, HCl,
chloroform, ethyl acetate, Na SO anhidrous, and
zeolite.All materials were analytical grade (E-Merck),
except for aquadest and aluminum foil.
structure to cue lure, the hydration reaction to break
the double bond on 3-butene-2-one group has been
conducted and resulting in 4-(4-hydroxyphenyl-3
methoxy)-4-hydroxy-2-butanone. The addition of
OH group is expected to further enhance the activity
2
4
-
–
of the compound as the attractant for fruit flies.
Tools
MATERIALS AND METHODS
Materials
The tools used in this research were
chemistryglasswareset, hotplate, analyticalbalance,

PRABAꢀATI et al., Orient. J. Chem., Vol. 34(4), 2197-2202 (2018)
2199
1
spatula, magnetic stirrer, HNMR spectroscopy
(
(
methoxy)-3-buten-2-one was carried out through
aldol condensation reaction, which involved an
addition of nucleophilic enolate ion from acetone on
aldehyde group in vanillin.The method referred to the
Agilent Teknologies 500 MHz), FTIR spectroscopy
SHIMADZU),UV-Visspectrophotometer(SHIMADZU
U-1800), and melting point apparatus.
7
research conducted by Pranowo et al., in a 1:8 mol
Procedures
ratio of vanillin and acetone, and with 30% NaOH as
a catalyst. The product obtained was some yellow
colored needle-shaped crystals, with a melting point
of 77-78°C.The mechanisms that occur was shown
in Figure 3.
The synthesis of 4-(4-Hydroxyphenyl-3-methoxy)-
3-ꢁuten-2-one
In a 250 mL erlenmeyer flask equipped with
an ice bath, 7.8 mL (0.1052 mol) of acetone were
mixed with 4 mL of 30% NaOH using magnetic stirrer
for 30 minutes. Then, the mixture was added with
2
g (0.0131 mol) of vanillin at room temperature.The
obtained sediment was added with 15 mL of ethanol,
stirred for 1 h and then left for 24 hours. Next, the
mixture was added with 20 mL of cold water and
1
1
5 g of ice, mixed for 30 min. and then acidified with
0% HCl. Afterwards, the solution was extracted
three times with 25 mL of chloroform. The organic
phase was then washed with 25 mL of aquadest,
followed by the addition of Na SO anhidrous.Lastly,
2
4
the solution was filtered and evaporated until a solid
substance was obtained.
The synthesis of 4-(4-hydroxyphenyl-3-methoxy)-
4
-hydroxy-2-ꢁutanone.
First,1 g of 4-(4-Hydroxyphenyl-3-methoxy)
3-buten-2-one, 10 mL aquabidest and 13.6 mL
-
ethanol were loaded into a three-neck rounded
flask.The mixture was refluxed until the temperature
o
reached 30 C. Afterwards, 0.5 g of zeolite catalyst
was added and the mixture was refluxed for
120 minutes.
Fig. 3. Aldol condensation reaction mechanism
The results of IR spectrum analysis
Theevaluationof4-(4-hydroxyphenyl-3-methoxy)-
showed the forming of ketone groups from
4-hydroxy-2-ꢁutanone as attractant
4
-(4-Hydroxyphenyl-3-methoxy)-3-buten-2-one.
Three Steiner traps containing cottons
wetted by four liquid drops of synthesized
-(4-hydroxyphenyl-3-methoxy group)-4-hydroxy
2-butanon were prepared. The traps were placed
in yard areas planted with guava and start fruit, in
the Klidon village, Sukoharjo, Sleman Yogyakarta.
After 24 h the trapped fruit flies were counted. The
presence of fruit files in the test area was previously
confirmed with the installation of methyl eugenol as
a positive control.
It was characterized by the shifting of absorption
-
1
4
-
from 2561.47 cm wavenumbers, the specific
vibration range for aldehyde C-H group in vanillin, to
-
1
2569.18 cm , the typical absorption of C-C group
after ketone group inclusion. In addition, a specific
absorption for aromatic compound at 1589.34
-
1
-1
cm and 1512.19 cm , also for methoxy group at
-
1
1100-1300 cm were observed.
The synthesis results of 4-(4-hydroxyphenyl-3-
methoxy)-4- hydroxy-2-ꢁutanone
RESULTS AND DISCUSSION
The synthesis of 4-(4-hydroxy-phenyl-3-
The synthesis results of 4-(4-Hydroxyphenyl-3-
methoxy)-3-ꢁuten-2-one
methoxy)-4-hydroxy-2-butanone was conducted
through the hydration reaction of 4-(4-Hydroxyphenyl-
3-methoxy)-3-buten-2-one, using zeolite catalysts.
The synthesis of 4-(4-Hydroxyphenyl-3-

PRABAꢀATI et al., Orient. J. Chem., Vol. 34(4), 2197-2202 (2018)
The reaction was intended to break double bonds
2200
in 3-buten-2-one functional group, so that the
final structure of the compound was similar to the
structure of cue lure, which had previously been
shown to act as fruit fly attractant.The reaction that
occurs was shown in Figure 4.
The double bond was broken to form new
single bond, and hydroxyl group was bonded to
C atom. As a result, the final compound contains
two hydroxyl groups, the probably active groups in
attractant.
Fig. 4.The hydration reaction of 4-(4-hydroxyphenyl-3
-methoxy)-3-ꢁuten-2-one
atoms of the carbon that attached to the ketone
group (alpha carbon). This was confirmed by the
result of FTIR spectrum analysis that shown the shift
of C-C wavenumber from ketone group, as indicated
by the absorption of carbonyl group from ketone at
Analysis by FTIR spectroscopy resulted in
a spectrum shown in Fig.5.The forming of hydration
reaction product, was confirmed with the presence
of aliphatic C-H absorption, which appeared
-
1
2569.18 cm wavenumbers.
-
1
sharper on 2939.52 cm wavenumbers. In addition,
the absorption of –OH group was shifted toward
The second peak appeared on the chemical
shift of 3.9 ppm, indicated the absorption of proton on
methoxy group that bonded to benzene. A methoxy
group was very easily detected because the group
appeared on the specific shift area of 3.2-3.8 ppm,
and a high singlet peak indicated the existence
-
1
3
448.72 cm wavenumbers.
1
Furtheridentificationwith HNMRspectroscopy
produced a spectrum shown in Figure 6.
8
of methoxy (O-CH ) compound. The third peak
3
Based on the spectrum, there were four
distinct proton environments.The first peak appeared
at 2.3 ppm, the chemical shift of protons on hydrogen
appeared on the chemical shift of 6,7-7.3 ppm, the
specific absorption area of proton-proton on benzene
ring. The absorption appeared in multiplet.
Fig. 5.The FTIR spectrum of 4-(4-hydroxyphenyl-3-methoxy group)-4-hydroxy-2-ꢁutanone
The last peak that appeared at 9.8 ppm was
the peak resulted from a hydroxyl proton bonded to
carbon group in the para position from phenol group.
The chemical shift of hydroxyl group appeared on the
upfield (more protected than hydroxyl groups bonded
to benzene ring (12.05 ppm)) due to the exixtence of
carbon atoms, the electron donor groups.Therefore,
the hydrogen peak appeared in the more protected
shift. A substitution of hydroxyl group from alkenes
bonded to benzene group, had been successfully
done. This was verified by the absence of peak on
the chemical shift area of 5.3-5.9 ppm, the shift area
8
of alkene protons that attached to benzene group.

PRABAꢀATI et al., Orient. J. Chem., Vol. 34(4), 2197-2202 (2018)
2201
1
Fig. 6.The HNMR spectrum of 4-(4- hydroxyphenyl-3-methoxy)-4-hydroxy-2-ꢁutanone
9
Thefruitfliesactivityassayof4-(4-hydroxyphenyl-
Muryati et al., havestudiedtheidentification
of many fruit flies species and their responses
to attractant made from methyl eugenol and cue
lure. It turns out that the species of B. albistrigata,
B. cucurbitae, and B. knowmore are interested in
cue lure, while the species of B. carambolae and B.
papayae on chilies and papaya as their host plants,
can only be caught by methyl eugenol. In this study,
the presence of fruit flies that flock and resting on
the synthesized compound indicates the presence of
fruit fly species that corresponds to the compound.
Further research is needed to identify those fruit
flies’ species that attracted to 4-(4-hydroxyphenyl
3
-methoxy group)-4-hydroxy-2-ꢁutanone
The number of fruit flies attracted to
methyl eugenol (as control) and 4-(4-hydroxyphenyl
-
3-methoxy)-3-Hydroxy-2-butanone was presented
in Table 1.
The results showed that the synthesized
compound had potential as an attractant for fruit
flies, as indicated by the presence of fruit flies on
4
-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2
butanone, prior to the installation on Steiner
pitfalls.
-
-
3-methoxy)-4-hydroxy-2-butanone.
From the data in Table 1, the number of
CONCLUSION
fruit flies attracted to the synthesized compound
was much less compared to methyl eugenol.
This is possibly because the concentration of
A compound with similar structure
to cue lure, namely 4-(4-hydroxyphenyl-3-methoxy)
-4-hydroxy-2-butanon has been successfully
synthesized through condensation reaction
between vanillin and acetone in alkaline condition
NaOH 30%), followed by the hydration reaction
using zeolite as catalyst with a yield of 60%. The field
test shows that the 4-(4- hydroxyphenyl -3-methoxy)
4
-(4-hydroxyphenyl-3-methoxy)-4-hydroxy-2-
butanon is not high enough to be detected by fruit
flies at a far distance area.
(
Taꢁle 1:Test results of fruit flies attractant
compound in pool
-
4-hydroxy-2-butanone is a potential attractant for fruit flies.
No The type of attractant
The total number
of fruit flies
ACkNOwLEDGEMENT
1
2
Methyl Eugenol
4-(4-hydroxy-phenyl-3-methoxy)
4-hydroxy-2-butanone
16
3
Thanks to the LPPM UIN Sunan Kalijaga
Yogyakarta for the research funding provided
through the HAKI Research Grants in 2016.
-
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