Phosphorus-nitrogen compounds: Reinvestigation of the reactions of hexachlorocyclotriphosphazene with 1,4-butane- and 1,6-hexane-diolsNMR studies of the products

Abstract

Reactions of hexachlorocyclotriphosphazene N3P3Cl6 (1) with 1,4-butane-(2) and 1,6-hexane-diols (3) in (1:1:2, 1:2:4, and 1:3:6) stoichiometries in THF solution at room temperature (r.t.) and under refluxing conditions yield a total of 15 products: two open chain, N3P3Cl5[O(CH2)(n)OH] (n = 4, 6) (4, 5), two mono-spiro, N3P3Cl4[O(CH2)(n)O] (n = 4, 6) (6, 7), two mono-ansa, N3P3Cl4[O(CH2)(n)O] (n = 4,6) (8, 9), two dispiro, N3P3Cl2[O(CH2)(n)O](2) (n = 4, 6) (10, 11), two spiro-ansa, N3P3Cl2[O(CH2)(n)O](2) (n = 4, 6) (12, 13), one tri-spiro, N3P3[O(CH2)(4)O](3) (14), two single-bridged, N3P3Cl5[O(CH2)(n)O]N3P3Cl5 (n = 4, 6) (15, 16), one double-bridged, N3P3Cl4[O(CH2)(6)O](2)N3P3Cl4 (17), and one tri-bridged, N3P3Cl3[O(CH2)(6)O](3)N3P3Cl3 (18) derivatives. Their structures have been elucidated by MS, P-31, and H-1 NMR spectroscopy. The results obtained, based on the synthesis, characterization, product types, and the relative yields, are compared with those of previous studies on the reactions of 1 with 1,2-ethane-, 1,3-propane-, 1,4-butane-, 1,5-pentane-, and 1,6-hexane-diols.