Reaction Pathways in the Thermolysis of (2-Oxyethyl-Methacryl)Pentachlorocyclotriphosphazene

Synthesis and Spectroscopy of N3P3X5OCHCH2(X = Cl, F, OCH3, OCH2CF3, N(CH3)2) and N3P3X4(OCHCH2)2(X = Cl, N(CH3)2). Correlations of Ultraviolet Photoelectron Spectroscopy and Nuclear Magnetic Resonance Data to Electronic and Geometrical Structure

“…Good yields of crude 8 were obtained; however, significant decomposition occurred during distillation. Rearrangements leading to decomposition have been noted for other persubstituted alkoxycyclophosphazenes. , The mechanism of the phosphazene−phosphazane rearrangement has recently been elucidated . The ionic intermediates that arise in the course of the rearrangement potentially could initiate polymerization of the vinyloxy moiety in 8 .…”

Poly[(vinyloxy)cyclophosphazenes]

“…The slow development of insolubility in the polymer obtained from the penta(methoxy) derivative ( 3 ) is consistent with the phosphazene−phosphazane rearrangement which is well-established for (methoxy)cyclophosphazene derivatives . We have demonstrated that the phosphazene−phosphazane rearrangement proceeds through a dissociative process, thus generating a reactive intermediate on the polymer chain which could lead to cross-linking. The formation of low molecular weight oligomers in the polymerization of the penta(trifluoroethoxy) derivative ( 4 ) may reflect a decreased reactivity of persubstituted cyclotriphosphzenes or chain transfer processes involving the fluoroalkoxy exocyclic unit.…”

“…Elimination of the oxo-bridged phosphazene dimer (Scheme ) is an endothermic event due to the rigidity of the cross-linked material. The first step in the phosphazene−phosphazane rearrangement of alkoxycyclophosphazenes involves heterolytic cleavage of a exocyclic carbon oxygen bond to give the N 3 P 3 Cl 5 O - species . A similar reaction in the second decomposition step of 7 would provide a oxyanion positioned to displace a N 3 P 3 Cl 5 + unit and form the observed oxo-bridged dimer.…”

Five- and six-membered spirocyclic cyclotriphosphazene derivatives with methacryloyl substituents on the spirocyclic ring

“…In the case of exocyclic groups containing an olefinic moiety, addition polymerization *Correspondence to: Christopher W. Allen reactions lead to organic backbone polymers with the inorganic ring system as a substituent [2,3]. We have recently focused on the synthesis and polymerization of cyclophosphazenes with methacrylates as the exocyclic group [4][5][6]. In the course of these investigations, it was discovered that the most convient of the methacrylate derivatives, the phosphazene derivative obtained from 2-hydroxyethyl methylmethacrylate, N 3 P 3 Cl 5 O(CH 2 ) 2 OC(O)C(CH 3 -‫ס‬CH 2 , undergoes a slow phosphazene-phosphazane rearrangement [5].…”

“…In the course of these investigations, it was discovered that the most convient of the methacrylate derivatives, the phosphazene derivative obtained from 2-hydroxyethyl methylmethacrylate, N 3 P 3 Cl 5 O(CH 2 ) 2 OC(O)C(CH 3 -‫ס‬CH 2 , undergoes a slow phosphazene-phosphazane rearrangement [5]. The preliminary report of the mechanism of this rearrangement indicated a firstorder process involving dissociation of the carbonoxygen bond linking the organic component to the phosphazene ring [5]. We are exploring routes to methacrylate monomers for which this process is obviated [6].…”