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Synthesis of 1-Butyl-3-
Methylimidazolium Derivatives
Austin Letcher &
Mathew Amundson
Dr. Duane Weisshaar &
Dr. Gary Earl
Overview
• Background
• Experimental
• Initial Synthesis Reaction
▫ Analysis by HNMR, CNMR, HPLC
• Anion Exchange Reaction
▫ Analysis by HNMR, CNMR, HPLC
• Conclusions
• Future Work
• Acknowledgements
• References
Background
Earl et al. developed green method for
quaternizing alkylamines using dimethyl
carbonate (DMC)1
Desire to expand scope to include aromatic
amines
Target 1-butyl-3-methylimidazolium salts for a
collaboration with Dr. Mary Berry’s (USD)
citrate encased nanoparticles
1-methylimidazole forms multiple products with
DMC2
Experimental
Initial Synthesis Reaction Conditions:
135℃, 20 hours, in a Parr pressure reactor, O2
purge by N2 sparge
Anion Exchange Reaction Conditions:
citric acid (monohydrate) refluxed in reaction
mixture from the Parr under N2 for 2 hours
Initial Synthesis
1-butylimidazole
dimethyl carbonate (DMC)
1-butyl-3-methylimidazolium methylcarbonate
2-carboxylate zwitterion
Initial Synthesis Analysis: 1HNMR
Initial Synthesis Analysis: 13CNMR
Initial Synthesis Analysis: HPLC
Anion Exchange:
+ CO2 + MeOH
+ H2O
Anion Exchange Analysis: 1HNMR
Anion Exchange Analysis: 13CNMR
Anion Exchange Analysis: HPLC
Conclusions
Quaternization reaction complete in 20 hrs with <1%
reactants
Mixture of desired imidazolium methylcarbonate quat
and 2-carboxylate zwitterion
“Tris”-citrate anion exchange completed cleanly in < 2
hours
Citrate product is a honey colored, viscous liquid
The zwitterion, like the methylcarbonate, reacts with
acids3
Citrate quat was desired by Dr Berry to have a pH~7
Citric acid (pKa1= 3.09, pKa2= 4.75, pKa3= 6.41)
NMR confirms bis product was isolated
Future Work
Acknowledgements
Augustana College
Brandon Gustafson
Marlys Vant Hul
NPURC
EPSCoR/BRIN
Research Colleagues
References
• 1 Earl, G. W.; Weisshaar, D. E.; Wineinger, D.; Moeckly, S.; Hanson,
M.; Uilk, J.; Rekken, B.; Villa, E.; Zierke, J. P. Quaternary
Methyl Carbonates: Novel Agents For Fabric Conditioning.
Journal of Surfactants and Detergents 2004, 8(4), 325-29.
• 2 Holbrey, J. D.; Reichert, M. W.; Tkatchenko, I.; Bouajila, E.;
Walter, O.; Tommasi, I.; Rogers, R. D. 1,3-
Dimethylimidazolium-2-carboxylate: the unexpected synthesis
of an ionic liquid precursor and carbine-CO2 adduct. Chem.
Comm. 2003, 28-29.
• 3 Smiglak, S; Holbrey, J. D.; Griffin, S. T.; Reichert, W. M.;
Swatloski, R. P.; Katritzky, A. R.; Yang, H.; Zhang, D.;
Kirichenko, K.; Rogers, R. D. Ionic Liquids Via Reaction of the
Zwitterionic 1,3-Dimethylimidazolium-2carboxylate With
Protic Acids. Overcoming Synthetic Limitations and
Establishing New Halide Free Protocols For the Formation of
ILs. Green Chem. 2007, 9, 90-98.

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Applied Science: Thermodynamics, Laws & Methodology.pdf
Applied Science: Thermodynamics, Laws & Methodology.pdfApplied Science: Thermodynamics, Laws & Methodology.pdf
Applied Science: Thermodynamics, Laws & Methodology.pdf
 

Imidazole presentation

  • 1. Synthesis of 1-Butyl-3- Methylimidazolium Derivatives Austin Letcher & Mathew Amundson Dr. Duane Weisshaar & Dr. Gary Earl
  • 2. Overview • Background • Experimental • Initial Synthesis Reaction ▫ Analysis by HNMR, CNMR, HPLC • Anion Exchange Reaction ▫ Analysis by HNMR, CNMR, HPLC • Conclusions • Future Work • Acknowledgements • References
  • 3. Background Earl et al. developed green method for quaternizing alkylamines using dimethyl carbonate (DMC)1 Desire to expand scope to include aromatic amines Target 1-butyl-3-methylimidazolium salts for a collaboration with Dr. Mary Berry’s (USD) citrate encased nanoparticles 1-methylimidazole forms multiple products with DMC2
  • 4. Experimental Initial Synthesis Reaction Conditions: 135℃, 20 hours, in a Parr pressure reactor, O2 purge by N2 sparge Anion Exchange Reaction Conditions: citric acid (monohydrate) refluxed in reaction mixture from the Parr under N2 for 2 hours
  • 5. Initial Synthesis 1-butylimidazole dimethyl carbonate (DMC) 1-butyl-3-methylimidazolium methylcarbonate 2-carboxylate zwitterion
  • 9. Anion Exchange: + CO2 + MeOH + H2O
  • 13. Conclusions Quaternization reaction complete in 20 hrs with <1% reactants Mixture of desired imidazolium methylcarbonate quat and 2-carboxylate zwitterion “Tris”-citrate anion exchange completed cleanly in < 2 hours Citrate product is a honey colored, viscous liquid The zwitterion, like the methylcarbonate, reacts with acids3 Citrate quat was desired by Dr Berry to have a pH~7 Citric acid (pKa1= 3.09, pKa2= 4.75, pKa3= 6.41) NMR confirms bis product was isolated
  • 15. Acknowledgements Augustana College Brandon Gustafson Marlys Vant Hul NPURC EPSCoR/BRIN Research Colleagues
  • 16. References • 1 Earl, G. W.; Weisshaar, D. E.; Wineinger, D.; Moeckly, S.; Hanson, M.; Uilk, J.; Rekken, B.; Villa, E.; Zierke, J. P. Quaternary Methyl Carbonates: Novel Agents For Fabric Conditioning. Journal of Surfactants and Detergents 2004, 8(4), 325-29. • 2 Holbrey, J. D.; Reichert, M. W.; Tkatchenko, I.; Bouajila, E.; Walter, O.; Tommasi, I.; Rogers, R. D. 1,3- Dimethylimidazolium-2-carboxylate: the unexpected synthesis of an ionic liquid precursor and carbine-CO2 adduct. Chem. Comm. 2003, 28-29. • 3 Smiglak, S; Holbrey, J. D.; Griffin, S. T.; Reichert, W. M.; Swatloski, R. P.; Katritzky, A. R.; Yang, H.; Zhang, D.; Kirichenko, K.; Rogers, R. D. Ionic Liquids Via Reaction of the Zwitterionic 1,3-Dimethylimidazolium-2carboxylate With Protic Acids. Overcoming Synthetic Limitations and Establishing New Halide Free Protocols For the Formation of ILs. Green Chem. 2007, 9, 90-98.