Synthesis and Structural Characterization of Singly, Doubly, and Triply Bridged Derivatives of Hexachlorocyclotriphosphazene with Bis(2-hydroxyethyl) Ether and 2,2-dimethylpropane-1,3-diol

Abstract

The reactions of hexachlorocyclotriphosphazene, N 3 P 3 Cl 6 (1), with 2,2-dimethylpropane-1, 3-diol (2), and bis(2-hydroxyethyl) ether (3) have been previously reported. Although both reactions gave the expected spiro, ansa, and bridged type products, open-chain and triply bridged derivatives from both systems and singly bridged derivatives from 2,2-dimethylpropane-1,3-diol (2) were not isolated, and doubly bridged compounds were only detected in trace amounts in both systems. However, in a subsequent reinvestigation in tetrahydrofuran (THF) solution, the reaction of 1 with the diols 2 and 3 gave the open chain PHOSPHORUS-NITROGEN COMPOUNDS 199The doubly bridged derivatives were also isolated in better yields relative to earlier reports. The substituted cyclotriphosphazenes have been characterized by elemental analysis, mass spectrometry, as well as by 1 H, 31 P, and 13 C NMR spectroscopy. It is found that with variation of the solvent there is a decrease in the product formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amount of products formed by intermolecular reactions (singly, doubly, and triply bridged derivatives) of cyclophosphazene.

Synthesis, structural, and stereogenic characterizations of new trispirocyclotriphosphazenes

“…[ 6 ] The reaction of HCCP with bidentate or polydentate reagents can yield different products such as spiro, ansa, bino, open chain, bridged, spiro‐bino‐spiro (sbs), and ansa‐spiro‐ansa (asa) and mixtures thereof. [ 7 ] Differences in reaction products may depend on the chain lengths of the bidentate or polydentate ligands used, the positions of the chemically active groups, whether the ligands are rigid or flexible, the polarities of the solvents, and the reaction conditions (base and temperature). [ 8 ] The chemical and physical properties of HCCP derivatives vary greatly with substituted side groups.…”

The Reactions of Octachlorocyclotetraphosphazene with Difunctional Bis(2-Hydroxyethyl) Ether. Nuclear Magnetic Studies of the Products

“…The reactions of difunctional reagents with both of the cyclophosphazenes (1 and 2) have been of significant interest because they lead to the formation of regioisomers in substitution reactions: spiro-, ansa-, bridged-derivatives and their mixtures. [39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54] The octachlorocyclophosphazene (1), is more reactive than the hexachlorocyclophosphazene (2); the former can also, in principle, give rise to a much larger number of products, and hence structure determination is more difficult. 2,19,51 The reactions of secondary amines, NHR 2 , gave mainly nongeminal products, although stoichiometry, reaction temperature, and solvent influence the nature of the products and their relative proportions.…”