Ansa versus spiro selectivity in substitution reactions of a mono ansa fluorodioxycyclotriphosphazene derivative with diols

Abstract

In this study, regio-selectivity in the nucleophilic substitution reactions of a mono ansa fluorodioxycyclotriphosphazene derivative with dials has been investigated. The cyclotriphosphazene derivative, N3P3Cl4[OCH2(CF2)(3)CH2O] (1), was reacted with the disodium salts of 1,3-propanediol andtetraethyleneglycol in THF solution at a 1:1 M ratio and eight new products (2-6, 7a, 7b and 8) were formed. These products were separated and characterized by elemental analysis, mass spectrometry, H-1 and P-31 NMR spectroscopy. The crystal structures of 2, 3, 5, 6 and 7a have been characterized by X-ray crystallography. The spiro derivatives (3, 6) were formed as the major product in the reactions of compound 1 with both diols. (C) 2015 Elsevier Ltd. All rights reserved.