UV-mediated thiol-ene click reactions for the synthesis of drug-loadable and degradable gels based on copoly(2-oxazoline)s.

An 80-membered library of gels composed of monofunctional 2-ethyl-2-oxazoline and 2-nonyl-2-oxazoline and one of four selected difunctional 2-oxazolines (containing either ether or ester bonds) were synthesized by microwave-assisted ring-opening polymerizations. The difunctional 2-oxazolines were prepared from the thiol-ene reaction of glycol dimercaptoacetate or 2,2'-(ethylenedioxy)diethanethiol and 2-but-3'-enyl-2-oxazoline or 2-dec-9'-enyl-2-oxazoline. 53 of the gels exhibited glass-transition temperatures, which ranged from -5.

Microwave-assisted cationic ring-opening polymerization of 2-oxazolines.

Unlike any other polymer class, the (co-)poly(2-oxazoline)s have tremendously benefited from the introduction of microwave reactors into chemical laboratories. This review focuses on the research activities in the area of (co-)poly(2-oxazoline)s prepared by microwave-assisted syntheses and, correspondingly, summarizes the current-state-of the-art of the microwave-assisted synthesis of 2-oxazoline monomers and the microwave-assisted ring-opening (co-)polymerization of 2-oxazolines as well as prominent examples of post-polymerization modification of (co-)poly(2-oxazoline)s. Special attention is attributed to the kinetic analysis of the microwave-assisted polymerization of 2-oxazolines and the discussion of non-thermal microwave effects.

Microwave-Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources.

The copoly(2-oxazoline) pNonOx80 -stat-pDc(=) Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9'-enyl-2-oxazoline Dc(=) Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources.

The π-Electron Delocalization in 2-Oxazolines Revisited: Quantification and Comparison with Its Analogue in Esters.

The single crystal X-ray analysis of the ester-functionalized 2-oxazoline, methyl 3-(4,5-dihydrooxazol-2-yl)propanoate, revealed π-electron delocalization along the N-C-O segment in the 2-oxazoline pentacycle to significant extent, which is comparable to its counterpart along the O-C-O segment in the ester. Quantum chemical calculations based on the experimental X-ray geometry of the molecule supported the conjecture that the N-C-O segment has a delocalized electronic structure similar to an ester group. The calculated bond orders were 1.