GREEN CHEMISTRY: MICROWAVE SYNTHESIS OF IONIC LIQUIDS
AND THEIR USE AS MEDIUM IN DIELS-ALDER REACTION
Anthony J. Lilienthal, Arthur J. Koudelka, Benjamin C. Haenni, and Gholam A. Mirafzal (Mentor)
College of Arts and Sciences, Department of Chemistry, Drake University
Abstract
The effectiveness of the substitution of ionic liquids for traditional aromatic solvents in the Diels-
Alder Reaction was investigated. Three methylimidazolium based ionic liquids – 1-butyl-3-
methylimdazolium bromide, 1-butyl-3-methylimidazolium iodide and 1-methyl-3-(p-toluene
sulfonyl)imidazolium chloride – were synthesized in the microwave and were then used as
solvents/catalysts in the Diels-Alder reaction between maleic anhydride and 1,3-cyclohexadiene.
The results presented here illustrate how ionic liquids are effective and recyclable solvents for the
Diels-Alder reaction.
Introduction
Ionic Liquids have been termed “Designer Solvents” 1 due to their variable physical properties.
Due to their low volatility and recyclability, they are also considered Green Solvents. Ionic
2 however, Microwave-Enhanced
liquids could offer students the opportunity to perform many chemical synthesis reactions without was demonstrated that [BMIM][Br] and [BMIM][I] could be synthesized in as little as 2 minutes.
using harsh, volatile organic solvents. The synthesis of a new ionic liquid and its effectiveness as a Similarly, [MPtolsIM][Cl] was synthesized via 2 minutes of microwave radiation (Scheme 1).
solvent for the Diels-Alder reaction between 1,3-cyclohexadiene and maleic anhydride is herein
described. In addition, the recyclability of another ionic liquid is also described.
Materials and Methods
Maleic anhydride, 1,3-Cyclohexadiene, 1-iodobutane, 1-bromobutane, 1-methylimidazole, and p-
toluenesulfonyl chloride were all purchased from the Sigma Aldrich company and were used
without any further purification.
FT-IR were performed neat on a Nicolet 510P Spectrometer. FID-GC were performed on an
H6890 series instrument, equipped with an HP-5 (Crosslinked 5% PH ME Siloxane) column with
30m x 0.32 mm x 0.25 μm film thickness. During the analyses of the Diels-Alder Reaction
products, the initial column temperature was 60°C (1 minute), which was then increased 10°C/min.
to 250°C (1 minute).
Experimental Procedure
Ionic Liquid Synthesis (Scheme 1)
Butylmethylimidazoluim Halide Ionic Liquid Synthesis:
15 mmoles of 1-bromobutane (or 1-iodobutane) and 15 mmoles of 1-methylimidizole (MIM) were
added to a small beaker and heated for 2 minutes (8 x 15 s.) at 10 % power in a SHARP Carousel
Microwave. The product was washed twice with diethyl ether to remove any possible remaining
reactants.
Methyl(p-toluenesulfonyl)imidazolium Halide Ionic Liquid Synthesis:
5 mmoles of p-toluenesulfonyl chloride and 20 mmoles 1-methylimidazole (MIM) were mixed (20
s.) into a slurry in a small beaker. The slurry was heated for 2 minutes (8 x 15 s.) at 10% power in
a SHARP Carousel Microwave. The product was washed three times (4 mL each) with diethyl
ether to remove any possible remaining reactants.
 
Diels-Alder Reaction
1.2 mmoles of maleic anhydride and a magnetic stirbar were added to a 10 mL round bottomed
flask. To this 6.0 mmoles of cyclohexadiene was added. Immediately following the addition of the
cyclohexadiene, 1.00 mL of the ionic liquid (1-butyl-3-methylimdiazolium bromide ([BMIM][Br]),
1-butyl-3-methylimidazolium iodide ([BMIM][I]), or 1-methyl-3-(p-toluenesulfonyl)imidazolium
chloride ([MPtsIM][Cl])) was added and the reaction was mixed at room temperature for 45
minutes. The Diels-Alder product was then separated from the ionic liquid by the addition of
equal volumes diethyl ether and water. This organic layer was analyzed via FID-GC to determine
the %conversion of maleic anhydride into the Diels-Alder Product (Scheme 2).
Recyclability Tests Diels-Alder Reaction with [PtolsMIM][Cl]
The aqueous layer, containing [BMIM][Br], was extracted from the Diels-Alder reaction mixture and was The effectiveness of 1-methy-3-(p-toluenesulfonone)imidazolium chloride ([PtolsMIM][Cl]) and
placed into a rotary evaporator with a 75°C hot water bath until only the viscous ionic liquid remained freshly synthesized [BMIM][Br] and [BMIM][I] was compared. The % conversion of the maleic
(approximately 2 hours). The ionic liquid ([BMIM][Br]) was then reused in the Diels-Alder Reaction anhydride from the [PtolsMIM][Cl] solvated reaction was 65.819% while the % conversion for
described. TLC and FT-IR were performed, confirming that the ionic liquid was not changed during the [BMIM][Br] and [BMIM][I] were 83.854% and 97.887% , respectively (Figure 1). The GC spectra
reaction. of the organic layers from each of the Diels-Alder reactions show corresponds with the previous
  results from the previous presentation, where maleic acid (converted from excess maleic anhydride
during the extraction) has a retention time of 9.324 minutes while the product has a retention time of
Results and Discussion 9.741 minutes. Even with it’s decrease % conversion, since the ionic liquid-solvated Diels-Alder
Ionic Liquid Synthesis reaction was performed at room temperature, it is still a more effective solvent than the volatile
Most ionic liquid synthesis procedures require too much time to be used for educational purposes; molecular solvents.
ionic liquid synthesis reduces the time required from hours to minutes. 3
It
Recyclability Tests
Since, in some situations, it is more efficient for the ionic liquids to be prepared before the students
attend the lab, a recyclable solvent would allow more ionic liquid to be conserved. It was concluded
Scheme 1: The General Equation of Microwave-Enhanced
Synthesis of methylimidazolium halide ionic liquids.
through TLC and FT-IR analysis that the removal of water from aqueous [BMIM][Br] is sufficient to
recycle bromide ionic liquid. [BMIM][Br] was able to solvate three repetitions of the Diels-Alder
a) [BMIM][Br] R = Butyl X = bromide reactions (Figure 2) using this recyclability procedure; moreover, the percent maleic anhydride
b) [BMIM][I] R = Butyl X = iodide
c) [MPtolsIM][Cl] R = P-toluenesulfonyl X = chloride
converted during the Diels-Alder reaction solvated by [BMIM][Br] actually increased as the
repetitions were performed. It is predicted that [BMIM][I] will have similar recyclability properties,
since the dehydration of aqueous layers containing [BMIM][I] also purified the compound and
[BMIM][I] has similar properties to [BMIM][Br]; however, more extensive experiments must be
performed in order more accurately describe the recyclability butylmethylimidazolium halide ionic
liquids as solvents for the Diels-Alder reaction.
 
% Maleic Anhydride Converted
Ionic Liquid DA Reaction 1 DA Reaction 2 DA Reaction 3
[BMIM][Br] 83.854 97.482 98.885
Figure 2
By comparing the IR spectra of the ionic liquids [BMIM][Br] and [MPtolsIM][Cl] with the 1-
Conclusion
Ionic liquids offer educators the opportunity to teach students without using hazardous, volatile
methylimidazole spectra, it was concluded that the diethyl ether washes were insufficient to remove the
organic solvents. Three methylimidazolium halide ionic liquids were successfully synthesized in 2
remaining 1-methylimidazole, since many of the 1-methylimidazole peaks were also present in the
minutes via microwave-enhanced synthesis; however, the 1-methyl-3-(p-
[MPtolsIM][Cl] spectra; however, indications of the ionic liquid product are still present. For example,
toluenesulfonyl)imidazolium chloride was unsuccessfully purified, which, at least partially,
the [MPtolsIM][Cl] spectra has peaks that are indicative of aromatic C= C bonds (1581.5 and 1455.5 cm -
accounted for its low maleic anhydride conversion rate during the Diels-Alder reaction. Even with
1
). These sharp peaks are observed on the [MPtolsIM][Cl] spectra, but not in the 1-methylimidazole
its decreased conversion rate, [PtolsMIM][Cl] was still a more effective solvent for the Diels-Alder
spectra and could not have indicated a contaminant p-toluenesulfonyl chloride. P-toluenesulfonyl
chloride’s role as the limiting reagent suggests that all the compound had reacted, and it is quite soluble in reaction, since classic solvents would require hours at high temperature for the reaction to go to
completion. Finally, the butylmethylimidazolium bromide ionic liquid were shown to be easily
diethyl ether. Another indicator of [MPtolsIM][Cl] is the broad peak at 1200 cm -1, which may suggest the
recyclable; multiple Diels-Alder reactions could be performed using the same ionic liquid, as long as
simultaneous presence of sulfnyl S=O bond and aromatic nitrogen, both of which have characteristic
the aqueous layer was evaporated prior to the repetition of the experiment.
peaks near 1180 cm-1 .3,4 Also, the S=O peak from the p-toluenesufonyl chloride peak is broad, which
would account for the width of the peak on the [MPtolsIM][Cl] spectra.
Future Work
We are currently experimenting to replace 1,3-cyclohexadiene with less volatile dienes, such as
% Maleic
Ionic anthracene. Also, the effect of ionic liquid solvation in other reactions will be investigated. Further
Anhydride
Liquid tests will be performed on the [PtolsMIM][Cl] to further purify it. After which, effectiveness in the
Converted
Diels-Alder reaction will be reassessed.
[BMIM][Br] 83.854
[BMIM][I] 97.887
Scheme 2
References
[MPtolsIM] 1
Yau, Hon Mau et al. “Ionic Liquids: Just Molten Salts After All?” Molecules. 2009, 14 (7) 2521-34.
65.819
[Cl] 2
Varma, Rajender S. "Expeditious Synthesis of Ionic Liquids using Ultrasound and Microwave Irradiation," Ionic Liquids as Green Solvents: Progress and
Prospects. Ed. Robin D. Rogers and Kenneth R. Seddon. Boston: American Chemical Society. (2003) 82-92.
Figure 1 3
Abdel-Wahab. M. F. et al, “Infrared Study of New Sulfonylurea Derivatives and Sulfonamides.” Analytical Chemistry. 1966, 38 (3) 508.
4Chatwal, Gurdeep R., “Application of Infrared Spectroscopy to Organic Compounds.” Spectroscopy. Himalaya Publishing House. (2009) 2.70.