New Highly Functionalized Primary Allyl, Hydroxyl, and Tosyl Poly(propylene glycol)s (PPG) from Available PPG Derivatization

Abstract

The more stringent reaction conditions used to optimize the synthesis of α,ω-di-O-(4-toluenesulfonyl)poly(propylene glycol) from commercial poly(propylene glycol) (PPG) of 2000 g/mol molar mass, compared to those applied for allowing the same modification on PEG, showed that the secondary hydroxyl end groups were less reactive than the primary ones. Thus, chemical end group transformations were successfully done on this polymer by introducing various groups, such as oxopropyl, carboxymethyl, allyl, 3-hydroxy-n-propyl, and 3-(4-toluenesulfonate)-n-propyl, on its terminal monomer units in order to enhance their reactivity. These reactions were optimized by adjustment of the reaction conditions to obtain fully α,ω-functionalized poly(propylene glycol)s. Particularly, the more reactive primary diallyl, dihydroxyl, and ditosyl poly(propylene glycol)s were obtained with very high functionality within experimental accuracy in a range ±0.1.

Synthesis of Electroneutralized Amphiphilic Copolymers with Peptide Dendrons for Intramuscular Gene Delivery

“…As compared to N 3 -PEG-N 3 in our previous work, PPG caused different synthetic methods (Scheme ). Particularly, NH 2 -PPG-NH 2 was used as the initial raw material for N 3 -PPG-N 3 preparation to avoid the interference with terminal groups, such as monohydroxy PPG . AE was simply translated into AE-CDI, and CDI was obviously demonstrated to be linked to AE due to the appearance of chemical shifts of number c, d, and e of hydrogen (Figures A and S2).…”

“…Particularly, NH 2 -PPG-NH 2 was used as the initial raw material for N 3 -PPG-N 3 preparation to avoid the interference with terminal groups, such as monohydroxy PPG. 40 AE was simply translated into AE-CDI, and CDI was obviously demonstrated to be linked to AE due to the appearance of chemical shifts of number c, d, and e of hydrogen (Figures 1A and S2). 1 H NMR analysis of the acquired product (Figure 1B) showed that the starting compound AE-CDI was absent (the NMR spectra of AE-CDI vs NH 2 -PPG-NH 2 in Figure 1A and C, respectively).…”

Improvement of Synthetic Vectors for Gene Therapy Using Ring‐Opening Cationic Polymerization

“…After subsequent hydroboration and hydroxylation, the diprimary hydroxytelechelic PPO was tosylated in the presence of triethylamine, giving in high yield and high specificity di-3-tosylpropyl telechelic PPO (28). The polymerization of 2-methyl-2-oxazoline was carried out using this functionalized PPO as initiator.…”

“…The copolymer which was synthesized was characterized by 1 H NMR spectroscopy and by SEC (28). As an average, the hydrophobic PPO segment had a degree of polymerization of 37, and a number of poly(2-methyl-2-oxazoline) units of 48 corresponding to an number average molar mass of 6200 Da.…”

“…However, careful analysis of the chain end functions according to ref. 28 showed that the sample was composed of around 70% (mole/mole) of triblock and 30 % of diblock.…”