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Microdroplets Accelerate Ring Opening of Epoxides

  • Yin-Hung Lai
  • Shyam Sathyamoorthi
  • Ryan M. Bain
  • Richard N. Zare
Research Article

Abstract

The nucleophilic opening of an epoxide is a classic organic reaction that has widespread utility in both academic and industrial applications. We have studied the reaction of limonene oxide with morpholine to form 1-methyl-2-morpholino-4-(prop-1-en-2-yl) cyclohexan-1-ol in bulk solution and in electrosprayed microdroplets with a 1:1 v/v water/methanol solvent system. We find that even after 90 min at room temperature, there is no product detected by nuclear magnetic resonance spectroscopy in bulk solution whereas in room-temperature microdroplets (2–3 μm in diameter), the yield is already 0.5% in a flight time of 1 ms as observed by mass spectrometry. This constitutes a rate acceleration of ~ 105 in the microdroplet environment, if we assume that as much as 5% of product is formed in bulk after 90 min of reaction time. We examine how the reaction rate depends on droplet size, solvent composition, sheath gas pressure, and applied voltage. These factors profoundly influence the extent of reaction. This dramatic acceleration is not limited to just one system. We have also found that the nucleophilic opening of cis-stilbene oxide by morpholine is similarly accelerated. Such large acceleration factors in reaction rates suggest the use of microdroplets for ring opening of epoxides in other systems, which may have practical significance if such a procedure could be scaled.

Graphical Abstract

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Keywords

Microdroplet Electrospray ionization Reaction acceleration Epoxide ring opening Microparticle imaging velocimetry 

Notes

Acknowledgments

We gratefully acknowledge the Air Force Office of Scientific Research through Basic Research Initiative grant (AFOSR FA9550-16-1-0113) for supporting this work.

Supplementary material

13361_2018_1908_MOESM1_ESM.docx (544 kb)
ESM 1 (DOCX 544 kb)

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Copyright information

© American Society for Mass Spectrometry 2018

Authors and Affiliations

  • Yin-Hung Lai
    • 1
  • Shyam Sathyamoorthi
    • 1
  • Ryan M. Bain
    • 1
  • Richard N. Zare
    • 1
  1. 1.Department of ChemistryStanford UniversityStanfordUSA

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