MICELLAR SOLUTIONS AS ALTERNATIVE

SOLVENT SYSTEMS FOR ORGANIC SYNTHESISKendall Craig, Laura Krings, and Heather Martin

Advisor: David Brownholland, Ph.DDepartment of Chemistry, Carthage College

Celebration of Scholars 2016: Exposition of Student & Faculty Research, Scholarship &Creativity

Results and DiscussionThe intermediate products were successfully synthesized withgood percent yields. The chemical shifts of the intermediates1H NMR spectra are consistent with the expected peaks, whichvalidated the identity and purity of the compounds (Figure 1).

The novel surfactant was not successfully obtained using theFisher esterification (step converting 11 into 12). Howeverwhile using a model substrate (7), the conversation wassuccessfully carried out under alternative reagents. Thisreaction combined N,N'-dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), and polyethylene glycolmethyl ether (PEG-500-M) with B-sitosterol succinate (7) toyield the product, 8, (Scheme 2). Analysis via 1H NMRconfirmed the product’s identity, as the observed chemicalshifts were consistent with expected absorbances3, andindicated acceptable purity (Figure 2).

AbstractOrganic synthesis produces a massive amount of solvent waste. Organic solvents are toxic, volatile,expensive to dispose of, and their use is unsustainable. A host of alternatives to organic solvent are underdevelopment, including solvent-free reactions, supercritical fluids, ionic fluids, and water. Ideally, themost environmentally friendly organic solvent substitute is low in energy costs, can be sustainablysynthesized, and is relatively abundant. The obvious candidate to fulfill the mentioned criterion is water.However, it is rarely compatible with organic reactions in terms of solubility and stability, thuspresenting limitations to its utility as an organic solvent. This research focuses on the use of micellarsolutions to manage these limitations. Micelles provide a medium for the organic reaction to occurwithin water – the product of which can then be extracted with minute amounts of organic solvent –reducing the amount of organic solvent waste produced. Micelles have even been shown to conduct somereactions more efficiently and at room temperature, thus lowering the energy costs involved in theseorganic syntheses. The aim of this study is to synthesize a micellar catalyst capable of immobilizingstarting materials or catalysts to the interior of the micelle. We report progress on the synthesis of a Δ22

steroidal-PEG surfactant derived from lithocholic acid.

Experimental

Figure 1. 1H NMR Spectra of 4.

Scheme 2. Model Reaction for Installation of PEG Headgroup.

Acknowledgements & ReferencesThis research was made possible by the funding of the Carthage College SURE Program. A special thanks goes to faculty advisor DavidBrownholland.1. Anastas, Paul T., and John Charles. Warner. Green Chemistry: Theory and Practice. Oxford: Oxford UP, 1998. Print. 2. Jimenez-Gonzales, C.; Curzons, A. D.; Constable, D. J. C.; Cunningham, V. L. The International Journal of Life Cycle Assessment 2004, 9, 114-1213. Klumphu, Piyatida, and Bruce H. Lipshutz. "“Nok”: A Phytosterol-Based Amphiphile Enabling Transition-Metal-Catalyzed Couplings in Water at Room Temperature." The Journal of Organic Chemistry J. Org. Chem. 79.3 (2014): 888-900. Web.

Future Directions• Finish the synthesis and ultimately evaluate the

utility of this novel surfactant• Improve the efficiency of the synthesis through

removing the purification step in the reaction of 2 to 3, reducing the amount of organic solvent using in purification and potentially increasing the overall yield of the synthesis.

Figure 2. 1H NMR of Novel Surfactant

Scheme 1 . Synthesis of a Δ22 steroidal-PEG surfactant derived from lithocholic acid. Percentyields are shown.