Term of Award

Spring 2021

Degree Name

Master of Science, Applied Physical Science

Document Type and Release Option

Thesis (open access)

Copyright Statement / License for Reuse

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.

Department

Department of Chemistry

Committee Chair

Hans Schanz

Committee Member 1

Karelle Aiken

Committee Member 2

Ji Wu

Abstract

The hydroamidation reaction is an attractive methodology for the construction of larger functional molecules. In our research, a baseline reactivity was established for the hydroamidation reaction using a set of N-alkyl and N-aryl (trifluoro)acetamides with methyl acrylate and acrylonitrile, various bases and varying reaction conditions. The combination of alkenes, acetamides, and trifluoroacetamides with base was crucial for reaction rate. N-aryl trifluoroacetamides exhibited near quantitative conversions in neat alkene with Diazabicycloundecene (DBU) as base. The less acidic N-aryl acetamides performed much faster in the presence of KOtBu and conversions of >95% were accomplished regularly but contained a large presence of side reactions, namely polymers formed during the reaction from methyl acrylate and acrylonitrile. N-aryl acetamides unexpectedly (>95%) and reliably reacted with acrylonitrile and DBU within an hour. Somewhat surprisingly, the amount of base did not always correlate with reaction rate. In fact, reactions with KOtBu often performed at similar rates between 10-25% loading with respect to amide but providing better yields with lower base concentrations. Alkyl acetamides and trifluoroacetamides exhibited significantly lower reaction rates and conversions with Hunig’s base which is weaker than DBU. Also, temperatures studies demonstrated that many reactions plateaued at elevated temperatures, while room temperature reactions frequently provided the highest conversions. This can partially be attributed to the degradation of base or side product formation resulting in an inhibition of the reaction. These trends were then used to establish reaction conditions to generate a polymer based on a bifunctional amide and acrylate. The polymerization affords approximately 8% conversion of the functionalities and improved designs are needed to obtain macromolecules of relevant size.

Research Data and Supplementary Material

No

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