The first substitution reactions of N,N-spiro bridged octachlorobiscyclotriphosphazene

Abstract

The reaction of the N,N-spiro bridged octachlorobiscyclotriphosphazene {N3P3Cl4[br-N(CH2)(5)CH3](2)N3P3Cl4} (1), in three (1:1 stoichiometries, 1:2 and 1:3.5), with the sodium derivative of 1,2-ethanediol in THF solution at room temperature produced five products, the mono-spiro derivative {N3P3Cl2[O(CH2)(2)O] [br-N(CH2)(5)CH3](2)N3P3Cl4} (2), cis and trans di-spiro derivatives {N3P3Cl2[O(CH2)(2)O][br-N(CH2)(5)CH3](2) [O(CH2)(2)O]N3P3Cl2} (3, 5), the ipsilaterat di-spiro isomer {N3P3[O(CH2)(2)O](2)[br-N(CH2)(5)CH3](2)N3P3Cl4} (4) and the tetra-spiro derivative {N3P3[O(CH2)(2)O](2)[br-N(CH2)(5)CH3](2)[O(CH2)(2)O](2)N3P3} , (6), whose structures have been characterized by elemental analysis, mass spectrometry, H-1 and P-31 NMR spectroscopy and X-ray crystallography. The nucleophilic substitution reactions of the N,N-spiro bridged octachlorobiscydotriphosphazene were investigated for the first time and X-ray crystallographic studies of all the structures (2-6) have been reported as the first examples of derivatives of this new class of ring system in the literature. (C) 2015 Elsevier Ltd. All rights reserved.