Efficient synthesis and RAFT polymerization of the previously elusiveN-[(cycloalkylamino)methyl]acrylamide monomer class

CO2-responsive polyacrylamide copolymer vesicles with acid-sensitive morpholine moieties and large hydrophobic RAFT end-group

“…Fragmentation Chain Transfer (RAFT) polymerization over other types of reversible deactivation radical polymerizations are well-documented, 1,15,16 and include its application to a wider range of monomers and lower reaction temperatures. RAFT allows the rapid synthesis of water-soluble multi-block polyacrylamides with high degrees of livingness and narrow molecular weight distributions (MWDs), [17][18][19] including polyacrylamides containing methylene substituted saturated nitrogen heterocycles. 19 The present article describes the efficient syntheses of unique amphiphilic di-and tri-block copolymers consisting of exclusively polyacrylamide blocks containing ionisable morpholine moieties that selfassemble into a variety of morphologies.…”

Poly(Boc-acryloyl hydrazide): the importance of temperature and RAFT agent degradation on its preparation

“…This degradation has been reported in the RAFT polymerisation of other acrylamide derivatives, 24,25 including closely related methacryloyl hydrazide, 26 with better control reported when the polymerisation is carried out at low temperatures. 25,27 This sidereaction is often overlooked in the polymerisation of primary and secondary acryl-and methacrylamides, and makes synthesising highly functional polymers from this type of monomers inherently challenging. 28 The need for greater control over these materials is more significant when looking to understand better the nature of the structure-activity relationship throughout post-polymerisation modification and biological screening.…”

Synthesis of N-[(dialkylamino)methyl]acrylamides and N-[(dialkylamino)methyl]methacrylamides from Schiff base salts: useful building blocks for smart polymers

“…[7][8][9] The N-dialkyl amino (including saturated nitrogen heterocycle) of substituted acrylamides and methacrylamides can be reversibly ionized allowing for a pH-response that alters polymer hydrophobicity. [9][10][11][12][13][14][15] Amphiphilic block copolymers comprising such monomers can self-assemble into a variety of nano-objects for use as stimuli-responsive polymersomes for targeted delivery of therapeutics. [11][12][13] In a recent communication, the synthesis of the selected acrylamides containing N-methylene saturated nitrogen heterocycles, and their incorporation into well-defined water-soluble block copolymer polyacrylamides was realised.…”

“…[11][12][13] In a recent communication, the synthesis of the selected acrylamides containing N-methylene saturated nitrogen heterocycles, and their incorporation into well-defined water-soluble block copolymer polyacrylamides was realised. 14 In this full paper, we expand on the monomer synthesis by providing efficient multi-gram routes to acrylamides and methacrylamides, including those with dialkyl acyclic and large saturated nitrogen heterocyclic rings. The synthesis involves efficient generation of the methylene Schiff base salt, which was characterized in the hydrated form.…”

“…Synthesis of N-[(cycloalkylamino)methyl]acrylamides 1a-3a,14 and N-[(cycloalkylamino)methyl]methacrylamides 1b-3b using the in situ Schiff base salt approach. Synthesis of methylene Schiff base salts 4a-4f characterised by 1 H NMR as hydrated derivatives 5a-5f.…”