Reinvestigations of the reactions of hexachlorocyclotriphosphazene with difunctional primary amines leading to novel dangler, ansa and bridged derivatives. Spectroscopic studies of the derived products

Abstract

In an extension of the research on the nucleophilic substitution reactions of hexachlorocyclotriphosphazene (1) with linear aliphatic primary diamines, NH2-(CH2)(n) -NH2 (n = 3, 5, 6 and 8) are surveyed. In the presence of pyridine, NaH and in excess of the used amine as base, at 0 degrees C and room temperature, we subjected the reactions of 1, to a systematic reinvestigation with aliphatic propane-1,3-, pentane-1,5-, hexane-1,6- and octane-1,8-diamines (2, 3, 4 and 5 respectively) and we isolated a total of 18 compounds which include examples of all four structural types (open chain, spiro, ansa and the bino derivatives). The novel synthesized open chain (6), mono-ansa (8a), spiro-ansa (10), single-bridged (12a), double-bridged (13a) and tri-bridged (14a) cyclophosphazene derivatives are reported for the first time. The synthesized compounds are characterized by elemental analysis, MS, FT-IR, H-1 and P-31 NMR spectroscopy. Spectroscopic data, product types and the relative yields are compared with those of the previously reported cyclophosphazene derivatives derived from di-functional nucleophilic reagents. (C) 2019 Elsevier B.V. All rights reserved.