Tunable Polymers Obtained from Passerini Multicomponent Reaction Derived Acrylate Monomers

Abstract

A new strategy to obtain functionalized acrylate monomers is introduced using the Passerini three-component reaction (Passerini-3CR). This straightforward one-pot synthesis is characterized by excellent atom economy and structurally diverse products. By using acrylic acid and a variety of aldehydes and isocyanides, a set of several acrylate monomers was synthesized. Subsequent free radical polymerization yielded polyacrylates with tunable properties depending on the used components for the Passerini reaction. For instance, by varying the aldehyde component from acetaldehyde to heptanal, control over the glass transition in the final polymer was achieved. Moreover, for highly polar acrylate monomers a thermoresponsive behavior (upper critical solution temperature; UCST) was observed in methanol and/or ethanol.

Potentially biocompatible polyacrylamides derived by the Ugi four-component reaction

“…Acrylic acid 1 (99%, Aldrich) was freshly distilled before use in Ugi-4CRs. Methyl 4-isocyanobutyrate 4d was synthesized according a procedure mentioned in several publications [40][41][42][43][44][45]. All solvents were used without any kind of purification.…”

“…The reaction conditions were adopted from our previous study polymerizing diversely substituted acrylate monomers [45]. In short, the polymerization was conducted in ethyl acetate at 70°C with 1.0 mol% AIBN as thermal initiator (Scheme 2).…”

Polymers with upper critical solution temperature behavior in alcohol/water solvent mixtures

“…Scheme 11 A series of polyacrylates (Scheme 12) were prepared by radical polymerization using functionalized acrylate monomers originated from the Passerini three-component reaction (Passerini-3CR) of acrylic acid and a variety of aldehydes and isocyanides as reported by Meier. [136] The properties of the 'Passerini' polyacrylates could be well tuned depending on the reagents used for Passerini reaction. Favored by balanced hydrophilicity/hydrophobicity, poly(1-(benzylamino)-1-oxopropan-2-yl acrylate) M a n u s c r i p t (PBAOPA) and poly(methyl 4-(2-(acryloyloxy)propanamido)butanoate) (PMAPAB) were found to exhibit UCST behavior in ethanol at 55−74 and 6−19 o C, respectively, while poly(methyl 4-(2-(acryloyloxy)propanamido)butanoate) (PMAPAB) and poly(1-(cyclohexylamino)-1-oxopropan-2-yl acrylate) (PCAOPA) exhibit UCST transitions in methanol at −37 to −20 and 6−27 o C respectively.…”

Dual side chain control in the synthesis of novel sequence-defined oligomers through the Ugi four-component reaction

“…The use of multicomponent reactions in the field of organic chemistry, for instance in the synthesis of pharmaceuticals, 29 hydrogels, 30,31 peniciline 55 scaffolds 32 and peptidomimetics 33 is already well established. 32 Recently, the use of the P-3CR and the U-4CR in polymer chemistry was demonstrated by our [34][35][36][37][38][39] and other groups. [40][41][42][43] Furthermore, sequential Ugi reactions were studied by Wessjohann et al for the synthesis of peptide-peptoid 60 chimeras 31,44,45 and in the synthesis of macrocycles.…”