Abstract
Chemical modification of cellulose is challenging due to its low reactivity and poor solubility. Halogenation followed by displacement reactions has been demonstrated to be a valuable strategy for appending new functionalities to the anhydroglucose rings of cellulose and cellulose derivatives. In this paper, we report a simple and efficient pathway to modify the inexpensive, commercial cellulose ether, hydroxyethyl cellulose (HEC). First, methanesulfonyl chloride (MsCl) in N, N-dimethyl formamide (DMF) can selectively chlorinate the terminal primary hydroxyl groups from hydroxyethyl cellulose (HEC), thereby affording high terminal chloride content. Then, the resulting chlorinated HEC undergoes displacement reactions with various nucleophiles including azide (NaN3), amine (1-methylimidazole), and thiols (3-mercaptopropionic acid and 2-mercaptoethanol). All products were characterized by NMR and FT-IR spectroscopic methods. Exploiting this strategy, we prepared a library of HEC derivatives, including cationic and anionic derivatives, which are of great interest in various applications including as surfactants, in gas separation membranes, and as crystallization inhibitors in amorphous solid dispersions for oral drug bioavailability enhancement.
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Acknowledgments
We thank the Institute for Critical Technology and Applied Science (ICTAS), the Macromolecules Innovation Institute (MII), and the Virginia Tech Departments of Sustainable Biomaterials and of Chemistry for their financial, facilities, and educational support. We thank Dr. Xiuli Li for providing insights regarding NMR data interpretation.
Funding
We gratefully acknowledge partial funding support of the work from the National Science Foundation through grant IIP-1827493 (SP), and through grant DMR-2204996 (KJE). This work was partially supported by GlycoMIP, a National Science Foundation Materials Innovation Platform funded through Cooperative Agreement DMR-1933525.
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All authors contributed to the study conception and design. Synthesis, characterization, and data interpretation and analysis, were performed by CG and SP. The first draft of the manuscript was written by CG and all authors contributed to the editing of the manuscript, including preparation of the final version. All authors read and approved the final manuscript.
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Gao, C., Petrova, S.P. & Edgar, K.J. Chlorination of hydroxyethyl cellulose enables selective functionalization. Cellulose 31, 1481–1495 (2024). https://doi.org/10.1007/s10570-023-05675-x
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DOI: https://doi.org/10.1007/s10570-023-05675-x