MICROWAVE

ASSISTED LIMONENE
EPOXIDATION
Daniela Jurado Betancur
Hctor Daniel Molina Eraso
Johnathan A. Ortega Meneses
Some generalities about the use of
microwaves
The main advantages of microwave assisted
organic synthesis
Faster reaction: the reactions are completed in few minutes instead of hours.
Better yield and higher purity: less formation of side product are observed using
microwave irradiation, and the product is recovered in higher yield. Consequently, also
the purification step is faster and easier.
Reproducibility: precise control of reaction parameters, such as temperature, pressure
and power. This leads always to reproduce the same reaction conditions
Easy to use: all the reactors and software are very easy to use and all reactions can be
easily moved fromconventional to microwave heating.
The solvent
The same solvent that is usually used in the conventional reaction can also be used with
microwave heating.
Polar solvents couple well with microwaves and reach high temperatures in a short
time.
Non-polar solvents are transparent to microwaves.
If it is obtained a non-polar mixture, a different treatment must be done.
Microwave at constant temperature - Microwave program
The microwave program when constant temperature is needed, usually consists of two
steps:
The ramp to reach the target temperature.
To keep the temperature for the desired reaction time
To avoid overheating the reactor, the maximum heating time for a reaction is one hour.
The ramp to reach the target temperature.
Small amount (up to 30 mL): the increasing of the temperature can be fixed in the rate
25C/min.
Large amount (more than 30 mL): the first step needs to be longer. In this case, its
advised an increase of 10C/min
Microwave power
The value of the maximum microwave power depends on the amount of sample and of
the number of reaction vessel.
Up to 30 mL of volume and/or up to three vessels, 400-500 Watt of microwave power is
enough to heat the reaction mixture.
When large volume or more than three reactors are used, its better to use an higher
value of power (about 700-800 watt).
If the temperature is not following the designed temperature profile, use longer
heating time and/or increase the power.
If during the heating ramp the temperature overshoots, reduce the value of
microwave power of about 100-150Watt.
If a very fast increase of temperature is noticed during the ramp-step of the
reaction (80-100C/min), immediately stop the microwave program. Probably one
reagent is highly reactive and the efficient microwave heating creates a large
exothermic effect in the reaction
Microwave at constant power
A microwave program at constant power can be used, but only with an open system.
Which chemistry is not suitable for microwave
Reactions that are extremely exothermic should not be performed in the instrument.
In those cases, the experiment can be performed at low concentration (very diluted
solution).
Table 1. Typical reaction conditions.
Variable Conditions [1] Conditions [2] Conditions [3]
Time 24 h - 8 h
Temperature 33 - 38 C 25 - 50 C 38 C
Catalyzer 0,1 g 0,04 g 0,1 g
Limonene 0,5 g 2 mmol 0,66 M
H2O2 0,83 g 0,46 g (30 wt.% in water) 1,33 M
Acetonitrile 3,2 g 3.0 ml 14,1 M
Flask Volume 8 ml 25 ml 25 ml

[1] Barrera Z., R.; Villa de P, A. L.; Montes de Correa, C. Kinetic Modeling of Limonene Epoxidation over PW-Amberlite. Ind.
Eng. Chem. Res. (2009), 48,647653.
[2] Villa de P, A. L.; Taborda, F.; Montes de Correa, C. Kinetics of Limonene Epoxidation by Hydrogen Peroxide on PW-
Amberlite. J. Mol. Catal. A (2002), 185, 269.
[3] Barrera Z., R.; Villa de P, A. L.; Montes de Correa, C.; Williams, C. T. In situ Fourier transform infrared spectroscopic
studies of limonene epoxidation over PW-Amberlite. Applied Catalysis A: General 365 (2009) 4247.
Effects of the initial concentrations already known:
1. At a given time limonene conversion increased with the amount of
catalyst.
2. The conversion decreases with the increase in limonene concentration.
3. The conversion of limonene increased with the amount of oxidant.
4. Water enhances the conversion of limonene.
5. The addition of epoxide delays the time of reaction. Epoxide poisons the
catalyst.
Table 2. Bibliographical research of the microwave
conditions in the organic synthesis.
Reaction Microwave Conditions Reference
Synthesis of
monoglycerylcetyldimethylammonium from
3-chloro-1,2-propanediol (CP) and N,N-
dimethylhexadecylamine (DMHA) in 2-
propanol solvent and in solvent-free
conditions
T: 95 C, 130 C, 185 C
Time: 30 min, 30 min, 6 min.
Maximal power: 200 W
Satoshi H., Motoki F., Koji T., Masahiko A., Nick S. (2010) .
Microwave specific effects in organic synthesis: A
proposed model from the solvent-free synthesis of
monoglycerylcetyldimethylammonium chloride.
Chemical Physics Letters 491, 244247
synthesis of nanocomposite polymers of -
cyclodextrin (-CD) and nitrogen-doped
carbon nanotubes (N-CNTs)
Time: 10 min, 15 min, 30 min.
Constant microwave power
output of 700 W.
Sello P., Edward N., Bhekie M., Sabelo M. (2014).
Microwave-induced synthesis ofb-cyclodextrin/N-
doped carbon nanotube polyurethane
nanocomposites for water purification. Physics and
Chemistry of the Earth 6769, 105110.
Styrene epoxidation reaction with molecular
O2 as an oxidant over a sulfated CoY-
doped ZrO2 solid catalyst
T: 120 C
Time: 30 min.
Non-pulsed power supply of
400 W
Beena T., Basha S. (2009). Microwave-assisted
epoxidation of styrene with molecular O2 over sulfated
CoYZrO2 solid catalyst. Catalysis Communications
11, 114117
Table 2. Bibliographical research of the microwave
conditions in the organic synthesis.
Reaction Microwave Conditions Reference
Extraction of phenolic-compounds in
Myrcus Leaves
(300-900 W)
Dahmoune F., Nayak B., Moussi K., Remini H., Madani K.
(2014). Optimization of microwave-assited extraction of
polyphenols from Myrtus communis L. leaves. Food
chemestry 585-595.
Epoxidation of Styrene with O
2
(400 and 800 W)
Tyagi B., Shaik B., Bajaj H.C. (2009). Microwave assited
epoxidation of styrene with molecular O
2
over sulfated Co-Y-
ZrO
2
solid catalyst, Catalysis communications, 114-117.
Epoxidation for Styrene with H
2
O
2
30 min
Guangjian W., Zhengwang L., Yiwu L., Guangqing L., Mingxia
X., Lei W. (2008). Epoxidation of styrene with hydrogen
peroxide over Mn- Ti- Al-MCM -41 molecular sieve under
microwave irradiation. Chinese journal of catalysis ,29(11),
1159-1164.
Oxidation of acenaphthenequinone to
1,8-naphthalic anhydride by hydrogen
peroxide
T: 60 C
Time: 1 h
The initial reaction power
was set at 400 W
Shidokht N., Khashayar G. (2014). Solvent and microwave
effects on oxidation of aromatic -diketones. Journal of
Industrial and Engineering Chemistry.
Synthesis of polydextrose using glucose
and sorbitol as substrates; water and
phosphoric acid as initiator and catalyst.
T: 120 C
Time: 2 minutes
Constant microwave
power output of 999 W
Haisong W., Yonghui S., Guowei L. (2014). Rapid
microwave-assisted synthesis of polydextrose and
identification of structure and function. Carbohydrate
Polymers 113, 225230.
Table 3. Bibliographical research for another solvent
Solvent Reference
Dicloromethane
Chloroformed
THF
Selective epoxidation of (+)-limonene employing methyltrioxorhenium as catalyst.
Journal of Molecular Catalysis A: Chemical 358 (2012) 159165.
Dicloroethane
Application of complex heteropolytungstates in limonene epoxidation by H2O2 in
biphasic medium. Catalysis Today 107108 (2005) 230234.
Acetonitrile
Clean limonene epoxidation using Ti-MCM-41 catalyst. Applied Catalysis A:
General 287 (2005) 227235.

Advance in the study of limonene epoxidation with H2O2 catalyzed by Cu(II)
complex heteropolytungstates. Catalysis Communications 26 (2012) 117121

Table 4. Experimental activities program.
Activity Date Objective
Catalyst Synthesis August 25
th
and 26
th
To know the experimental
procedure to synthesize the
catalyst and to his further
application.
Catalyst Characterization Between September 1
st
and 4
th
.
To analyze how much efficient
could be the performance of this
catalyst when the reaction takes
place.
Reaction without microwaves August 26
th
and 27
th
To make a comparison of the
reaction yields and the benefits
which could have the
participation of the microwaves.
Reaction assisted by microwaves Between September 1
st
and 4
th
.
Additional References
Favretto L. (2004). Basic Guidelines for Microwave Organic Chemistry Applications.
Milestone Srl.