A general, selective synthesis of ω-hydroxyethenyl ethers

Degradation in Order: Simple and Versatile One‐Pot Combination of Two Macromolecular Concepts to Encode Diverse and Spatially Regulated Degradability Functions

“…which was optimized using e-caprolactone (CL) as monomer. 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) was selected as the basic organocatalyst to promote the ROP of CL at rt [18] and in THF to yield vinyl ether oligoCL with controlled length and complementary chain-ends.V inyl ethers are in fact stable under basic conditions and ab asic catalyst was necessary to prevent side reactions of the initiator to form cyclic acetals (Scheme S1) [19] or premature SGP, [20] while allowing the synthesis of the envisioned vinyl ether oligoCL at rt. Changing the reaction conditions from basic to acidic by addition of an excess (3 equiv to TBD) of the Brønsted acid diphenyl phosphate (DPP) to the polymerization mixture,e asily resulted in switching from ROPt oS GP.T he vinyl ether oligoCLs were therefore,t he heterotelechelic macromonomers undergoing acid-catalyzed SGP between the complementary chain-ends.T he mechanism is aMarkovnikov direct addition of the -OH to the CH 2 = CHO-producing acetal bonds.…”

New Amphiphilic Glycopolymers Based on a Polycaprolactone‐maleic anhydride Copolymer Backbone: Characterization by 15N NMR and Application to Colloidal Stabilization of Nanoparticles

“…Oligocaprolactones were fully characterized by 1 H, 13 C NMR and FT‐IR spectroscopy and MALDI‐ToF MS. It is afore to mention that, when using the ω ‐hydroxy vinyl ethers, care must be taken with the equilibrium between the ether and the corresponding saturated acetal (2‐methyl‐1,3‐dioxepane)32 as easily evidenced in the 1 H NMR spectrum by peaks at 1.29, 3.44 and 4.67 ppm. The proportion between the vinyl ether and the acetal depends on the concentration and naturally would interfere with the average degree of polymerization.…”

“…It is afore to mention that, when using the v-hydroxy vinyl ethers, care must be taken with the equilibrium between the ether and the corresponding saturated acetal (2-methyl-1,3-dioxepane) [32] as easily evidenced in the 1 H NMR spectrum by peaks at 1. This equilibrium has already been reported in the literature, although not clearly ascertained, in view of unexpected Raman spectra.…”

Synthesis of oligocaprolactone vinyl ether macromonomers and their use for indomethacin encapsulation in polymer nanoparticles based on polycaprolactone macromonomer–maleic anhydride–N‐vinyl pyrrolidone terpolymers

“…It deserves note that, when using the ω‐hydroxy vinyl ethers, care must be taken with the equilibrium between these ethers and the corresponding saturated acetal,19 as depicted in Scheme , and easily evidenced by the peaks at 1.29, 3.44 and 4.67 ppm (Fig. 1).…”