Synthesis and structural characterization of geminal and non-geminal 1,1,3,3-tetramethylguanidine substituted derivatives of cyclotriphosphazene: Thermal and spectroscopic investigations of the products

Abstract

The reactions of hexachlorocyclotriphosphazene, N₃P₃Cl₆ (1) with 1,1,3,3-tetramethyl-guanidine (2) in (1:1:2, 1:2:4 and 1:3:6) stoichiometries in THF and dichloromethane solutions under reflux yield a total of 4 novel products: three non-geminal derivatives, N₃P₃Cl₄[NCN₂(CH₃)₄]₂ (3), N₃P₃Cl₃[NCN₂(CH₃)₄]₃ (4) and N₃P₃Cl₂[NCN₂(CH₃)₄]₄ (5); and one hexa-substituted product, N₃P₃[NCN₂(CH₃)₄]₆ (6). The structures of 3-6 have been determined mainly by elemental analysis, MS, ³¹P and ¹H NMR spectral data. Furthermore, thermal characteristics of the synthesized compounds 4 and 6 were evaluated using Differential Scanning Calorimetric (DSC) measurements. NMR spectroscopic data, product types and relative yields are compared with those of the previously investigated derivatives of N₃P₃Cl₆ (1) with mono and difunctional reagents.

Graphical Abstract

Keywords:

• Phosphazene
• tetramethylguanidine
• geminal product
• nongeminal product
• Differential Scanning Calorimetry

Acknowledgments

We are grateful to Bilecik Seyh Edebali University for their financial support (Grant no: BAP 2016-01.BŞEÜ.04-02). We are indebted to the School of Chemistry, Southampton University, Middle East Technical University and GYTE for obtaining MS, DSC and NMR measurements. Finally, the authors wish to express gratitude to Prof. Dr. Simon Coles for his helpful suggestions and insight during this research studies.

Disclosure statement

No potential conflict of interest was reported by the authors.