New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+) as a Green Solid Catalyst

*Lahouaria Medjdoub  -  Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Exact and Applied Sciences, University of Oran1 Ahmed BenBella, BP 1524 El M'Naouar, 31000 Oran, Algeria
Belbachir Mohammed  -  Laboratory of Polymer Chemistry, Department of Chemistry, Faculty of Exact and Applied Sciences, University of Oran1 Ahmed BenBella, BP 1524 El M'Naouar, 31000 Oran, Algeria
Received: 14 Jun 2016; Published: 20 Aug 2016.
Open Access Copyright (c) 2016 Bulletin of Chemical Reaction Engineering & Catalysis
License URL:

Citation Format:
Cover Image

Nucleophilic substitution on hexachlorocyclotriphosphazene (HCCTP) with allylamine in order to give hexa(allylamino)cyclotriphosphazene (HACTP)  is performed for the first time under mild conditions by using diethylether as solvent to replace benzene which is very toxic. The reaction time is reduced to half and also performed at room temperature but especially in the presence of an eco-catalyst called Maghnite-H+. This catalyst has a significant role in the industrial scale. In fact, the use of Maghnite is preferred for its many advantages: a very low purchase price compared to other catalysts, the easy removal of the reaction mixture. Then, Maghnite-H+ is became an excellent catalyst for many chemical reactions. The structure of HACTP synthesized in the presence of Maghnite-H+ to 5% by weight is confirmed by 1H-NMR, 13C-NMR, 31P-NMR (Nuclear magnetic resonance) and FTIR (Fourier Transform Infrared spectroscopy). MALDI-TOF (Matrix-Assisted Laser Desorption/Ionisation-time-of-flight mass spectrometry) is used to establish the molecular weight of HACTP which is 471 g/mol. DSC (Differential Scanning Calorimetery) and TGA (Thermogravimetric Analysis) show that HACTP is a crystalline product with a melting point of 88 °C. It is reactive after melting but is degraded from 230 °C. Copyright © 2016 BCREC GROUP. All rights reserved

Received: 28th September 2015; Revised: 5th December 2015; Accepted: 4th January 2016

How to Cite: Medjdoub, L., Mohammed, B. (2016). New Method for Nucleophilic Substitution on Hexachlorocyclotriphosphazene by Allylamine Using an Algerian Proton Exchanged Montmorillonite Clay (Maghnite-H+) as a Green Solid Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2): 151-160 (doi:10.9767/bcrec.11.2.541.151-160)


Article Metrics: (click on the button below to see citations in Scopus)

cited by count 

Keywords: Hexachlorocyclotriphosphazene; Allylamine; Nucleophilic substitution; Maghnite-H+; NMR spectroscopy; Thermal properties

Article Metrics:

  1. Isıklan, M., Asmafiliz N., Özalp, E.E., Ilter, E.E., Kılıç, Z., Çosut, B., Yesilot, S., Kılıç, A., Öztürk, A., Hökelek, T., Koç, L.Y., Akyüz, L.E. (2010). Phosphorus-nitrogen compounds. 21. Syntheses, structural investigations, biological activities, and DNA interactions of new N/O spirocyclic phosphazene derivatives. The NMR behaviors of chiral phosphazenes with stereogenic centers upon the addition of chiral solvating agents. Inorganic Chemistry, 49: 7057-7071.
  2. Asmafiliz, N., Kılıç, Z., Öztürk, A., Hökelek, T., Koç, L.Y., Açık, L., Kısa, Ö., Albay, A., Üstündag, Z., Solak, A.O. (2009). Phosphorus-nitrogen compounds. 18. Syntheses, stereogenic properties, structural and electrochemical investigations, biological activities, and DNA interactions of new spirocyclic mono- and bisferrocenylphosphazene derivatives. Inorganic Chemistry, 48: 10102-10116.
  3. Elmas, G., Okumuş, A., Kılıç, Z., Hökelek, T., Açık, L., Dal, H., Ramazanoğlu, N., Koç, L.Y. (2012). Phosphorus-nitrogen compounds. Part 24. Syntheses, crystal structures, spectroscopic and stereogenic properties, biological activities, and DNA interactions of novel spiro-ansa-spiro- and ansa-spiro-ansa-cyclotetraphosphazenes. Inorganic Chemistry, 51: 12841-12856.
  4. Chandrasekhar, V., Thilagar, P., Pandian, B.M. (2007). Cyclophosphazene-based multi-site coordination ligands. Coordination Chemistry Reviews, 251: 1045-1074
  5. Uslu, A., Coles, S.J., Davies, D.B., Esen, M., Hursthouse, M.B., Kılıç, A. (2010). Effect of gem 2,2′-disubstitution and base in the formation of spiro- and ansa-1,3-propandioxy derivatives of cyclotriphosphazenes. Inorganica Chimica Acta, 363: 3506-3515
  6. Li, Z., Qin, J. (1979). Synthesis of C60-containing polyphosphazenes from a new reactive macromolecular intermediate: Polyphophazene azides. Journal of Polymer Science, Part A: Polymer Chemistry, 42:194-199
  7. Li, Z., Qin, J., Xu, X. (2004). New approaches for the synthesis of hindered C60-containing polyphosphazenes via functionalized intermediates. Journal of Polymer Science, Part A: Polymer Chemistry, 42: 2877-2885.
  8. Singh, A., Krogman, N.R., Sethurman, S., Nair, L.S., Sturgeon, J.L., Brown, P.W., Laurencin, C.T., Allcock, H.R. (2006). Effect of side group chemistry on the properties of biodegradable L-alanine cosubstituted polyphosphazenes. Biomacromolecules, 7: 914-918.
  9. Greish, Y.E., Bender, J.D., Lakshmi, S., Brown, P.W., Allcock, H.R., Laurencin, C.T. (2005). Low temperature formation of hydroxyapatite-poly(alkyl oxybenzoate)phosphazene composites for biomedical applications. Biomaterials, 26: 1-9.
  10. Brunton, S. A., Stibbard, J. H. A., Rubin, L. L., Kruse, L. I., Guicherit, O. M., Boyd, E. A., Price, S. (2008). Potent Inhibitors of the Hedgehog Signaling Pathway. Journal of Medicinal Chemistry, 51: 1108-1110.
  11. Çosut, B., Hacıvelioglu, F., Durmus, M., Kılıç, A., Yesilot, S. (2009). The synthesis, thermal and photophysical properties of phenoxycyclotriphosphazenyl-substituted cyclic and polymeric phosphazenes. Polyhedron, 28: 2510-2516.
  12. Allcock, H.R. (2006). Recent developments in polyphosphazene materials science. Current Opinion in Solid State Materials Science, 10: 231-240.
  13. Gleria, M., Jaeger, R.D. (2004). Phosphazenes a worldwide insight. Nova Science Publishers Incorporation, Hauppauge, New York.
  14. Allcock, H.R., Napierala, M.E., Cameron, C.G., O’Connor, S.J.M. (1996). Synthesis and Characterization of Ionically Conducting Alkoxy Ether/Alkoxy Mixed-Substituent Poly(organophosphazenes) and Their Use as Solid Solvents for Ionic Conduction. Macromolecules, 29: 1951-1956.
  15. Xu, G., Lu, Q., Yu, B., Wen, L. (2006). Inorganic polymer phosphazene disulfide as cathode material for rechargeable lithium batteries. Solid State Ionics, 177: 305-309.
  16. Allcock, H.R., Wood, R.M. (2006). Design and synthesis of ion-conductive polyphosphazenes for fuel cell applications: Review. Journal of Polymer Science, Part B. Polymer Physics, 44: 2358-2368.
  17. Li, Z., Qin, J., Li, S., Ye, C., Luo, J., Cao, Y. (2002). Polyphophazene Containing Indole-Based Dual Chromophores: Synthesis and Nonlinear Optical Characterization. Macromolecules, 35: 9232-9235.
  18. Christova, D., Ivanova, S. D., Velichkova, R. S., Tzvetkova, P., Mihailova, P., Uzunov, I., Lakov, L., Peshev, O. (2003). Organic–inorganic composites based on cyclotriphosphazene-cross-linked PHEMA networks. Designed Monomers and Polymers, 6: 11-21.
  19. Belbachir, M. (2001). US Patent. 066969.0101.
  20. Belbachir, M., Bensaoula, A. (2001). Composition and method for catalysis using bentonites. US Patent. US6274527.
  21. Kuan, J. F., Lin, K. F. (2004). Synthesis of Hexa(allylamino)cyclotriphosphazene as a reactive fire retardant for unsaturated polyesters. Journal of Applied Polymer Science, 91: 697-702.

  1. Phosphorus–nitrogen compounds. Part 42. The comparative syntheses of 2-cis-4-ansa(N/O) and spiro(N/O) cyclotetraphosphazene derivatives: spectroscopic and crystallographic characterization, antituberculosis and cytotoxic activity studies
    Arzu Binici, Aytuğ Okumuş, Gamze Elmas, Zeynel Kılıç, Nagehan Ramazanoğlu, Leyla Açık, Hülya Şimşek, Beste Çağdaş Tunalı, Mustafa Türk, Remziye Güzel, Tuncer Hökelek, New Journal of Chemistry, vol. 43, no. 18, pp. 6856, 2019. doi: 10.1039/C9NJ00577C