Premium
Metal‐Free Fast Azidation by Using Tetrabutylammonium Azide: Effective Synthesis of Alkyl Azides and Well‐Defined Azido‐End Polymethacrylates
Author(s) -
Wang ChenGang,
Chong Amerlyn Ming Liing,
Lu Yunpeng,
Liu Xu,
Goto Atsushi
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903188
Subject(s) - azide , alkyl , halide , toluene , polymer chemistry , chemistry , copolymer , solvent , materials science , polymer , combinatorial chemistry , organic chemistry
An effective method to synthesize azido‐end polymethacrylates from tetrabutylammonium azide (BNN 3 ) in a nonpolar solvent (toluene) was developed. Several low‐mass alkyl halides were reacted with BNN 3 in toluene as model reactions and the rate constants of these reactions were determined, to confirm fast BNN 3 azidation for tertiary and secondary halides. The end‐group transformation of halide‐end polymethacrylates was effective and nearly quantitative. Notably, the combination of organocatalyzed living (or reversible deactivation) radical polymerization and BNN 3 azidation enabled the metal‐free synthesis of azido‐end polymethacrylates, including single‐azido‐end and multi‐azido‐end functional homopolymers and block copolymers. The rapid and quantitative reaction without the requirement for a large excess of BNN 3 , metal‐free and polar‐solvent‐free nature, and broad polymer scope are attractive features of this azidation.