Preparation of Poly(alkylene H-phosphonate)s and Their Derivatives by Polycondensation of Diphenyl H-Phosphonate with Diols and Subsequent Transformations

A new method of preparation of poly(alkylene H-phosphonate)s ( 1 ) by polycondensation of diphenyl H-phosphonate with diols such as 1,10-decanediol or tetra(oxyethylene) glycol is described. These polymers can be converted into poly(alkylene phosphate)s mimicking backbones of nucleic acids and other biomacromolecules. The described method is the only one allowing simple preparation of this important class of polymers. This method eliminates the major side reaction taking place when dialkyl H-phosphonates are used and is related to the C-alkylation and formation of the unreactive ether end groups. Reaction of diphenyl H-phosphonate with alcohols is practically irreversible and can be performed without removing phenol, formed as a byproduct of condensation. It can be carried out in solvent or in bulk at temperature 80−200 °C. Removing phenol enhances, however, formation of polymers with higher M̄ n . Polymers with M̄ n ∼ 30 × 10 3 were obtained and characterized as such or in the form of their derivatives. Chlorination of 1 with gaseous Cl 2 leads to corresponding poly(alkylene chlorophosphate)s transformed readily into further derivatives, for instance, poly(alkyl alkylene phosphate)s, poly(alkylene phosphate) salts, or/and acids, using the poly(alkylene phosphorimidazolide) as the reactive intermediate.