Preparation of a New Type of Phosphazene High Polymers Containing 2,2‘-Dioxybiphenyl Groups

Abstract

The direct reaction of [NPCl2] n with the difunctional reagent 2,2‘-dihydroxybiphenyl (HOC6H4C6H4OH) and K2CO3 in tetrahydrofuran gave soluble linear phosphazene high polymers instead of the expected cross-linked products. The reaction of [N3P3Cl6] with 1, 2, or 3 equiv of HOC6H4C6H4OH and K2CO3 in acetone gave the known spiro derivatives [N3P3Cl4(O2C12H8)], [N3P3Cl2(O2C12H8)2], and [N3P3(O2C12H8)3] without formation of bridging products, and the dichloro derivative reacted directly with para-substituted phenols HOC6H4R and K2CO3 in acetone to give the new compounds [N3P3(OC6H4R)2(O2C12H8)2] (R = Br, COC6H5, or OCH3), without signs of replacement of the bis(aryloxy) substituents. In an analogous manner, poly(dichlorophosphazene) [NPCl2] n reacted with HOC6H4C6H4OH and K2CO3 in THF without significant cross-linking to give, depending on the mole ratio, the soluble polymer [NP(O2C12H8)] n (M w = 450 000, T g = 160 °C) or the partially substituted polymers {[NP(O2C12H8)]0.35[NPCl2]0.65} n . The latter were subsequently reacted with the para-substituted phenols HOC6H4R and K2CO3 in THF to give the random copolymers {[NP(O2C12H8)]0.35[NP(OC6H4R)2]0.65} n [R = Br, CN, COCH3, or COC6H5). The new polymers are soluble (except the CN derivative, which was sparingly soluble) white solids, with only a few ppm of unreacted chlorine, and Mw of the order of 1 000 000 with polydispersities varying from 3 to 10. The T g values varied with R ranging from 73 °C (R = CN) to 54 °C (R = COMe).

Tailored Control and Optimisation of the Number of Phosphonic Acid Termini on Phosphorus‐Containing Dendrimers for the Ex‐Vivo Activation of Human Monocytes

“…= 6 th N 3 P 3 -cored analogues: To the best of our knowledge, the controlled substitution of functionalised phenol on polyphosphazene rings has been scarcely reported. [28] Nevertheless, starting from the versatile hexachloro-cyclo(triphosphazene), one can expect to substitute selectively one to six chlorine atoms. Assuming that selectivity would strongly depend on the nucleophile/base pair, the solvent, the temperature and the concentration, we have developed a strategy based on these assumptions to design cyclo(triphosphazene) dendritic cores presenting one to five aromatic aldehydes.…”

Polymer/Trimer/Metal Complex Mixtures as Precursors of Gold Nanoparticles: Tuning the Morphology in the Solid-State

“…The starting materials [NP(O2C12H8)]n [15] (with a Mw of 600,000) and N3P3(O2C12H8)3 [15] were prepared using the reported methods. The well known complex AuCl(PPh3) was prepared in high yield by adding AuCl (Aldrich) to a dichloromethane solution of PPh3 (1:1 in moles) and evaporating the solvent.…”

Immobilized redox enzymatic catalysts: Baeyer–Villiger monooxygenases supported on polyphosphazenes

“…1 unit (U) of PAMO oxidizes 1.0 μmol of phenylacetone to benzyl acetate per minute at pH 9.0 and 25 ºC in the presence of NADPH. Polyphosphazenes 1 [38,39], 2-4 [40], and 5 [18] were synthesized as previously described. Tetrahydrofuran (THF) was treated with KOH and distilled twice from Na in the presence of benzophenone.…”

“…The synthesis of polymers 5-7 (Scheme 1) was achieved as previously described starting from polyphosphazene 1 [38,39], by selective nitration with a sulfonitric mixture at room temperature during 1.5 h [40], followed by reduction with Lalancette's reagent [41] under reflux of THF (see Experimental). The composition and structure of the products was confirmed by the analytical and spectroscopic data.…”