Download Micellar Catalytic Effect of Cetyltrimethylammonium Bromide

International Journal of Engineering & Technology IJET-IJENS Vol: 12 No: 01
1
Micellar Catalytic Effect of Cetyltrimethylammonium Bromide on
O-Allylation of Eugenol by Allyl Bromide
Hernawan1*, Bambang Purwono2, Tutik Dwi Wahyunngsih2
1
Technical Implementation Unit for Development of Chemical Enginering Processes,
INDONESIAN INSTITUTE OF SCIENCES,Yogyakarta, 55861, Indonesia
2
Department of Chemistry, Faculty of Mathematics and Natural Sciences,
GADJAH MADA UNIVERSITY, Yogyakarta, 55281, Indonesia
Abstract
A simple and effective O-allylation reaction controlled micellar catalyst system was designed and synthesized. In this system,
cetyltrimethylammonium bromide (CTAB) was used for micellar catalytic O-allylation of eugenol. The reaction was carried out at
room temperature to avoid Claisen rearrangement product. The results showed that the optimum concentration of CTAB as a catalyst
was 1.21 × 102 mM with a yield 81.10%. GC-MS chromatogram revealed the major product is 4-allyl-1-(allyloxy)-2-methoxybenzene
with 93.30% conversion. The applications of CTAB on the micellar catalytic O-allylation of eugenol were effective to reduce the
reaction temperature and diminish the Claisen rearrangement product.
Keywords : cetyltrimethylammonium bromide, eugenol, micellar catalytic, O-allylation
I. INTRODUCTION
E
ugenol,
2-methoxy-4-(2-propenyl)
phenol
is
a
phytochemical obtained from Eugenia ceryophyllata
Thumb. It finds wide applications ranging from perfumeries,
flavourings, and in medicines [1]. Its derivatives 4-allyl-1(allyloxy)-2-methoxybenzene or allyl eugenil ether (AEE) is
an important intermediet in the synthesis of variety of fine or
special chemicals such as pharmaceuticals, agrochemicals,
dyes, flavors, fragrances, polimers, etc.
Generally
4-allyl-1-(allyloxy)-2-methoxybenzene
is
prepared by ether Williamson reaction or O-allylation via
direct allylation by the use of allyl bromide in acetone in the
presence of potassium carbonate. However, problems arise
when the O-allylation reaction with eugenol. This reaction is
ether compounds formation which requires heat conditions but
in eugenol it will followed by Claisen rearrangement reaction.
Because of that the use of heat on allylation of eugenol should
be avoided. To avoid using heat, reaction could be conduct in
room temperature, since reaction of ether formation involves
two phase, so reaction could be done by phase transfer catalyst
or micellar catalyst.
Previous research that has been done by Suryanto [2] and
Ningsih [3] showed that reflux at low temperature (56oC) were
able to cause Claisen rearrangement. For that reason, we
consider the use of surfactant (quarternary ammonium
bromide salt) as catalyst in this reaction. There are several
advantages of the catalyst system, such as an increased
reaction rate and mild reaction condition (temperature and
pressure), avoiding the employment of expensive anhydrous
or aprotic solvent [4].
Micellar catalysis is an effective means to accelerate
organic reactions between oil and water phase reactants. The
application of micellar systems or other organized molecular
assemblies has been recognized for many years, and they have
been exploited in many areas, such as the chemical and energy
industries in materials science, and in medicine [5-9] In
micellar catalysis system, lipophilic reactants are solubilized
in the surfactant micelles, and the swelling micelles disperse
in water phase containing hydrophilic reactants, so that the
reaction interface area between oil and water phase reactants is
enlarged greatly. The interface magnifying effect as well as
electrostatic interaction and concentrating effect result in
dramatic increases of reaction rates [10,11]. In addition,
micellar catalysis can make reaction conditions gentle, can
effectively inhibit side reactions to occur, and can enhance the
efficiency of organic synthesis
The aim of this study was to evaluate the application of
quarternary
ammonium
bromide
salt
especially
cetyltrimethylammonium bromide (CTAB) on the synthesis of
eugenol derivatives, 4-allyl-1-(allyloxy) -2-methoxybenzene.
II. MATERIAL AND METHODS
Chemical Reagents and Apparatus
Eugenol (2-methoxy-4-(2-propenyl) phenol) (Sigma, p.s).
NaOH, allyl alcohol 99%, HBr 47%, H2SO4 97%, NaCO3,
CaCl2, dicloromethane, cetyltrimethylammonium bromide
(CTAB), were purchased from Merck. All other reagents and
solvents were of analytical grade and were used as provided.
NMR spectra were recorded on a JEOL JNM-MY60 and
JEOL JNM ECA-500 spectrometers using CDCl3 as the
solvent with tetramethylsilane (TMS) as an internal standard.
Gas Chromatography – Mass Spectrometry (GC-MS)
experiments were performed on a GC-MS, Shimadzu QP2010S with Electron Impact 70 Ev. The experiments were
performed on Rastek RXi-5MS column, ø 0.25 mm x 30 m. IR
Spectra were recorded on Shimadzu Prestige-21.
Preparation of allyl bromide
Allyl bromide was prepared according Kamm and Marvel
[12] methods with slight modification. Into the 250 mL threeneck flask which is equipped with magnetic stirrer, drip
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International Journal of Engineering & Technology IJET-IJENS Vol: 12 No: 01
Preparation of allyl eugenil ether (2)
A mixture of eugenol (1, 16.4 g, 0.1 mol), NaOH (6 g,
0.15 mol), dicloromethane (50 mL), CTAB (2.75 x 10-1 mM),
and distilled water (50 mL) were placed in 500 mL round
bottom flask. Then allyl bromide (24.2 g, 0.2 mol) was added
dropwise. The mixture was stirred at room temperature for 5
h. After completion of the reaction the organic layer and water
were separated. Water layer was extracted with
dichloromethane (2 x 20 mL). The combined organic phase
was washed with distilled water (2 x 50 mL), dried with
anhydrous Na2SO4 and evaporated under reduced pressure.
Experiments conducted with various concentrations of CTAB
(5.49 x 10-1, 1.1, 6.04 x 10, 1.21 x 102, 1.81 x 102 mM). Dry
residue was analyzed by an IR, 1H-NMR,13C-NMR and GCMS spectrometers.
III. RESULT AND DISCUSSION
Table 1.
CTAB catalyzed O-allylation of eugenol with allyl bromide in
oil-water biphasic system
CTAB
Conversion (%)
Yield
Weight [CTAB]
(%)
E
AEE
AE
(g)
(mM)
0.005 2.75x10-1
11.20 77.70
22.30
0
0.01
5.49x10-1
16.20 76.40
23.60
0
0.02
1.10x100
19.50 68.81
31.19
0
1.1
6.04x101
69.50 16.30
83.70
0
2.2
1.21x102
81.10
5.30
93.30
1.40
3.3
1.81x102
81.00
6.10
93.00
0.90
Note : E= eugenol, AEE= allyl eugenil ether (2), AE= allyl
eugenol
Synthesis of allyl bromide was conducted by reacting
allyl alcohol with 47% hydrogen bromide with concentrated
sulfuric acid as catalyst. The result obtained is clear distillate,
strong smelling, refractive index of 1.475, density of 1.402 g
/mL and yield of 93% with boiling point 71oC [13]. The 1HNMR (CDCl3, 60 MHz) of the product showed the presence of
5 protons in the molecule: δ 6.00 ppm (1H, multiplet), δ 5.30
ppm (1H, singlet), δ 5.15 ppm (1H, doublet,), δ 3.99 ppm (2H,
doublet). IR υmax(cm-1): 3086, 2962-2870, 1635, 1442, 987 and
925 and 686.
In a preliminary study, the O-allylation reaction was
carried out in oil-water biphasic system in the presence of
CTAB without heating. As shown in Table 1, in the presence
2.75 × 10-1 mM of surfactant (CTAB), the O-allylation
reaction proceeded very slowly, the yield was less than
11.20% after 5 h, and the conversion was only 22.30%.
Reaction performed with CTAB (its critical micelle
concentration, CMC, in pure water at 25 °C is 9.20 × 10-1 mM
[14,15]) at a concentration of 1.21 × 102 mM (132CMC)
proceeded very rapidly, the yield reached 81.10% in same
time (5 h), and the conversion increased to 93.30%
Product Percentage (%)
funnel, thermometer, and condenser, HBr 47% (125 g, 84.5
mL) was placed. Then H2SO4 97% (37.5 g, 20 mL) was added
dropwise while stirring. After that allyl alcohol 99% (29 g, 34
mL) was added dropwise and then followed by addition of
H2SO4 97% (37.5 g, 20 mL) dropwise and remain in a state of
rotating stirrer. The mixture was left for 60 minutes. After
completion, reflux was continued by distillation at 70oC and
the distillate was collected in an ice bath. Distillate was moved
into the separating funnel and washed with 100 mL water and
extracted with 100 mL of Na2CO3 solution 5% (w/v). The
organic layer (bottom) were taken off and dried with
anhydrous CaCl2. The filtrate distillated again at 70oC and
allyl bromide was collected in a flask cooled in an ice bath.
Allyl bromide was weighed, checked for refractive index and
density. The structure was analyzed by IR and 1H NMR
spectrometers.
2
CM
132 CMC
Log [CTAB]
Figure 1. Influence of CTAB concentration on O-allylation of
eugenol (■) yield, (♦) conversion
Figure 1 shows the effects of CTAB concentration on the
O-allylation reaction. When CTAB concentration was below
CMC, the yield after 5 h was only 11.20%, the conversion was
about 22.30%, and hardly varied with surfactant
concentration. However, the yield and the conversion
increased with an increase in the surfactant concentration
higher than CMC, and leveled off after the surfactant
concentration reached 132CMC.
Quarternary base could served as phase transfer catalyst
but from this results show that CTAB reaction through
micellar catalyst. The experimental facts distinctly display the
high efficiency of micellar catalysis system. When surfactant
concentration is below CMC, the reaction system is a
suspension (under stirring) with two phases, and the reaction
rate is very slow. However, when surfactant interface energy
between oil and water phase is very small, so micelles were
formed. Eugenol was solubilized into the micelles after the
sodium hydroxide added in the form of eugenolic ion.
Interface area of oil /water phase was magnified suddenly and
the rate of O-allylation reaction occurring at the interface was
accelerated abruptly, so the conversion showed a break point
at CMC (Fig. 2). Above CMC, the number of micelles
increased with the increasing surfactant concentration, so the
rate of O-allylation reaction speeded up and a higher
conversion was obtained. Further increase of the surfactant
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International Journal of Engineering & Technology IJET-IJENS Vol: 12 No: 01
concentration induced micelles to expand, which in turn
caused slow increase of oil/water interfacial area. Therefore, at
high CTAB concentration, the rate of reaction increase
gradually but it will be slowed down at 1.21 x 102 mM and the
conversion of eugenol did not change significantly
3
ACKNOWLEDGMENT
The authors would like to express their gratitude to
Head for Indonesian Institute of Sciences which gave fund to
study and this research. Ir. Suharto, MT (UPT BPLM
Lampung) for providing the eugenol.
REFERENCES
O
[1]
Na+
[2]
O
O
Br
O
[3]
aqueous
[4]
dichloromethane
[5]
Figure 2. Mechanism of O-allylation of eugenol with allyl
bromide in oil-water biphasic system
[6]
[7]
Product obtained by the reaction is yellowish liquid, with
strong smelling. IR υmax (cm-1): 3078, 2908-2839, 1843, 1589
and 1512, 1458, 1419, 1226 and 1141, 995, 918, 856 and739.
The absence of absorption at 3400-3500 cm-1 showed no
absorption of OH groups, It was an indication that the reaction
of O-allylation certainly take place effectively at room
temperature in the presence of CTAB as micellar catalyst. 1HNMR (CDCl3, 500 MHz) of the product showed the presence
of 16 protons in the molecule : δ 6.71 ppm (3H, multiplet), δ
5.95 ppm (2H, multiplet), δ 5.26 ppm (2H, multiplet), δ 5.05
ppm (2H, triplet), δ 4.57 ppm (2H,doublet), δ 3.81 ppm (3H,
singlet), δ 3.31 ppm (2H, doublet). 13C-NMR (CDCl3, 125
MHz) revealed the presence of 13 carbons in the molecule :
39.80, 55.81, 69.96, 112.20, 113.58, 115.61, 117.73, 120.33,
133.03, 133.55, 137.62, 146.30, 149.36 ppm.
Further analysis using GC-MS gives molecular ion peak
at m/z 204 and base peak at m/z 163. The value shows the
molar mass of 4-allyl-1-(allyloxy)-2-methoxybenzene (2).
Based on FT-IR, 1H-NMR and GC-MS analysis, it can be
concluded that the product is 4-allyl-1-(allyloxy)-2methoxybenzene (2)
IV. CONCLUSION
The result show that reaction O-allylation catalyzed by
CTAB as micellar catalyst to eugenol can occurred at room
temperature without heating. The optimum concentration of
CTAB as catalyst was 1.21 × 102 mM with yield of 81.10%
and conversion 93.30% .The application of CTAB as micellar
catalyst on the O-allylation of eugenol can lowering the
reaction temperature and diminish the Claisen rearrangement
product. Further research can be done to use another types of
surfactants such as SDS, NP-10 and TTAB as catalysts in the
reaction.
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Hernawan, born in Gunungkidul, May 8th, 1982.
Elementary school until high school education was
completed in Gunungkidul. Obtained a bachelor's degree
in chemistry in 2005 and Master degree in Organic
Chemistry acquired in 2011 from Gadjah Mada
University, Yogyakarta, Indonesia.
Since 2006 he was worked as researcher in
Technical Implementation Unit for Development of
Chemical Engineering Processes, Indonesian Institute of
Sciences. In 2009 obtained a scholarship from
Indonesian Institute of Sciences Scholarship to continue
her master degree. Current research interest on the use of natural product and
derivatization with focus on molecules engineering through chemical
reactions, kinetics and thermodynamics of the reaction, separation and
purification as well as its functional activity.
Hernawan, S. Si, M. Sc is currently listed as a member of the
Indonesian Chemical Society and Indonesian Nanotechnology Society.
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International Journal of Engineering & Technology IJET-IJENS Vol: 12 No: 01
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Bambang Purwono received Ph.D from the University
of New South Wales, Sydney, Australia in 2000.
Currently he is lecturer in Department of Chemistry,
Universitas Gadjah Mada Yogyakarta, Indonesia since
1987. His research interests include synthesis of organic
chemistry and natural products.
Drs. Bambang Purwono, M.Sc, Ph.D is currently listes as
as amember of Indonesian Chemical Society
Tutik Dwi Wahyuningsih received the BSc and Master
degrees in Chemistry from Gadjah Mada University,
Indonesia, and the Ph.D degree on Synthesis and
Reactivity of Some New Activated Indoles from the
School of Chemistry, Faculty of Science, The University
of New South Wales, Australia. She is currently with
Gadjah Mada University Yogyakarta, Indonesia. Her
current interests include organic synthetic of essential oil,
green chemistry and oleochemistry.
Dra. Tutik Dwi Wahyuningsih, M.Si, Ph.D is currently listes as as
amember of Indonesian Chemical Society
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