Presentación de Resultados 26.08.2014

8/11/2019 Presentacin de Resultados 26.08.2014

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MICROWAVE

ASSISTED LIMONENEPOXIDATION

Daniela Jurado BetancurHctor Daniel Molina Eraso

Johnathan A. Ortega Meneses


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Some generalities about the umicrowaves


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The main advantages of microwave assisorganic synthesis

Faster reaction: the reactions are completed in few minutes instead of hou

Better yield and higher purity: less formation of side product are obmicrowave irradiation, and the product is recovered in higher yield. Consethe purification step is faster and easier.

Reproducibility:precise control of reaction parameters, such as temperatand 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 reaceasily moved from conventional to microwave heating.


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The solvent

The same solvent that is usually used in the conventional reaction can also microwave heating.

Polar solvents couple well with microwaves and reach high temperaturtime.

Non-polar solvents are transparent to microwaves.

If it is obtained a non-polar mixture, a different treatment must be done.


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Microwave at constant temperature - Microwave p

The microwave program when constant temperature is needed, usually costeps:

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


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The ramp to reach the target temperatu

Small amount (up to 30 mL): the increasing of the temperature can be fix25C/min.

Large amount (more than 30 mL): the first step needs to be longer. In tadvised an increase of 10C/min


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Microwave power

The value of the maximum microwave power depends on the amount of sathe number of reaction vessel.

Up to 30 mL of volume and/or up to three vessels, 400-500 Watt of microwenough to heat the reaction mixture.

When large volume or more than three reactors are used, its better to uvalue of power (about 700-800 watt).


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If the temperature is not following the designed temperature profile, uheating time and/or increase the power.

If during the heating ramp the temperature overshoots, reduce themicrowave power of about 100-150 Watt.

If a very fast increase of temperature is noticed during the ramp-streaction (80-100C/min), immediately stop the microwave program. Proreagent is highly reactive and the efficient microwave heating createxothermic effect in the reaction


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Microwave at constant power

A microwave program at constant power can be used, but only with an open


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Which chemistry is not suitable for micro

Reactions that are extremely exothermic should not be performed in the in

In those cases, the experiment can be performed at low concentration solution).


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Table 1. Typical reaction conditVariable Conditions [1] Conditions [2] Co

Time 24 h - Temperature 33 - 38 C 25 - 50 C

Catalyzer 0,1 g 0,04 g

Limonene 0,5 g 2 mmol

H2O2 0,83 g 0,46 g (30 wt.% in water)

Acetonitrile 3,2 g 3.0 ml

Flask Volume 8 ml 25 ml

[1] Barrera Z., R.; Villa de P, A. L.; Montes de Correa, C. Kinetic Modeling of Limonene Epoxidation over PW

Eng. Chem. Res.(2009), 48,647653.

[2] Villa de P, A. L.; Taborda, F.; Montes de Correa, C. Kinetics of Limonene Epoxidation by Hydrogen Perox

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 spe

studies of limonene epoxidation over PW-Amberlite.Applied Catalysis A: General365 (2009) 4247.


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Effects of the initial concentrations already k

1. At a given time limonene conversion increased with the amou

catalyst.

2. The conversion decreases with the increase in limonene conc

3. The conversion of limonene increased with the amount of oxid

4. Water enhances the conversion of limonene.

5. The addition of epoxide delays the time of reaction. Epoxide p

catalyst.


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Table 2. Bibliographical research of the micrconditions 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., MasahMicrowave specific effects in o

proposed model from the solve

monoglycerylcetyldimethylam

Chemical Physics Letters

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.,

Microwave-induced synthesis o

doped carbon nanotube

nanocomposites for water purifiChemistry of the Earth 67

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). Mic

epoxidation of styrene with molec

CoYZrO2 solid catalyst. Cataly

11, 114117


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Table 2. Bibliographical research of the micrconditions in the organic synthesis.

Reaction Microwave Conditions Reference

Extraction of phenolic-compounds in

Myrcus Leaves

(300-900 W)

Dahmoune F., Nayak B., Moussi K., Rem(2014). Optimization of microwave-ass

polyphenols fromMyrtus communis L

chemestry 585-595.

Epoxidation of Styrene with O2 (400 and 800 W)

Tyagi B., Shaik B., Bajaj H.C. (2009). Mic

epoxidation of styrene with molecular O2ZrO2 solid catalyst, Catalysis communic

Epoxidation for Styrene with H2O2 30 min

Guangjian W., Zhengwang L., Yiwu L., Gu

X., Lei W. (2008). Epoxidation of styren

peroxide over Mn- Ti- Al-MCM -41 mole

microwave irradiation. Chinese journal o

1159-1164.

Oxidation of acenaphthenequinone to

1,8-naphthalic anhydride by hydrogen

peroxide

T: 60C

Time: 1 h

The initial reaction power

was set at 400 W

Shidokht N., Khashayar G. (2014). Solven

effects on oxidation of aromatic -dik

Industrial and Engineering Ch

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

microwave-assisted synthesis of po

identification of structure and functio

Polymers 113, 225230


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Table 3. Bibliographical research for another

Solvent Reference

Dicloromethane

Chloroformed

THF

Selective epoxidation of (+)-limonene employing methyltrioxorhenium

Journal of Molecular Catalysis A: Chemical 358 (2012) 1591

DicloroethaneApplication of complex heteropolytungstates in limonene epoxidatio

biphasic medium. Catalysis Today107108 (2005) 230234

Acetonitrile

Clean limonene epoxidation using Ti-MCM-41 catalyst.Applied C

General 287 (2005) 227235.

Advance in the study of limonene epoxidation with H2O2catalyzed

complex heteropolytungstates. Catalysis Communications26 (2012


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Table 4. Experimental activities prog

Activity Date Objec

Catalyst Synthesis August 25th and 26th

To know the e

procedure to s

catalyst and

applic

Catalyst Characterization Between September 1st and 4th.

To analyze how

could be the per

catalyst when the

plac

Reaction without microwaves August 26th and 27th To make a com

reaction yields a

which could

participation of tReaction assisted by microwaves Between September 1st and 4th.


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Additional References

Favretto L. (2004). Basic Guidelines for Microwave Organic Chemistry ApMilestone Srl.

Presentación de Resultados 26.08.2014

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