Novel acrylamido monomers with higher hydrophilicity and improved hydrolytic stability: I. Synthetic route and...

The novel acrylamido monomer reported by our group (N-acryloylaminoethoxyethanol, AAEE; Chiari et al., Electrophoresis 1994, 15, 177-186), found to combine high hydrophilicity with extraordinary resistance to alkaline hydrolysis, has come under closer scrutiny due to unexpected and random autopolymerization while stored as a 1/1 v/v water solution at 4 degrees C (possibly due to a greater oxidability of the ether group). We have additionally found a unique degradation pathway of the monomer, called "1-6 H-transfer", by which the C1 (on the double bond site), by constantly ramming against the C6, next to the ether oxygen (O7, which in fact favors the transfer of the hydrogen atom by C1), produces radicals which more efficiently add to the monomer favoring autopolymerization and cross-linking. A number of novel monomers is proposed while maintaining the other unique characteristics of AAEE. One of them, N-acryloylaminopropanol, offers all the unique, special qualities of AAEE, without the noxious aspects of autopolymerization. Additionally, a synthetic route was optimized, yielding an essentially pure product in a single reaction step, with a yield > 99% and an equivalent purity (> 99%). The synthesis consists in reacting acryloyl chloride at -40 degrees C in presence of a twofold molar excess of aminopropanol and in ethanol (instead of methanol) as solvent. Other solvents, as well as the use of triethylamine for neutralizing the HCl produced, were found to give a variety of undesired byproducts.