3 years ago

Solvent-Selective Reactions of Alkyl Iodide with Sodium Azide for Radical Generation and Azide Substitution and Their Application to One-Pot Synthesis of Chain-End-Functionalized Polymers

Solvent-Selective Reactions of Alkyl Iodide with Sodium Azide for Radical Generation and Azide Substitution and Their Application to One-Pot Synthesis of Chain-End-Functionalized Polymers
Atsushi Goto, Chen-Gang Wang
Herein, a new reaction of an alkyl iodide (R–I) with an azide anion (N3) to reversibly generate the corresponding alkyl radical (R) is reported. Via this new reaction, N3 was used as an efficient catalyst in living radical polymerization, yielding a well-defined polymer–iodide. A particularly interesting finding was the solvent selectivity of this reaction; namely, R–I and N3 generated R in nonpolar solvents, while the substitution product R–N3 was generated in polar solvents. Exploiting this unique solvent selectivity, a one-pot synthesis of polymer–N3 was attained. N3 was first used as a catalyst for living radical polymerization in a nonpolar solvent to produce a polymer–iodide and was subsequently used as a substitution agent in a polar solvent by simply adding the polar solvent, thereby transforming the polymer–iodide to polymer–N3 in one pot. This one-pot synthesis was further applied to obtain N3-chain-end-functionalized polymer brushes on the surface, uniquely controlling the N3 coverage (number density). Using the chain-end N3, the obtained linear and brush polymers were connected to functional molecules via an azide–alkyne click reaction. The attractive features of this system include facile operation, access to unique polymer designs, and no requirement for using excess NaN3. In addition to N3, thiocyanate (SCN) and cyanate (OCN) anions were also studied.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05879

DOI: 10.1021/jacs.7b05879

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.