Phosphazene synthesis

More examples of phosphazene synthesis by the reaction of carbon tetrachloride with primary amine derivatives of phosphines have appeared ... 

Staudinger reaction (phosphazene synthesis and reactions with a special focus on the aza-Wittig process)and reviews of the applications of the aza-Wittig reaction to heterocyclic... 

H.R. Allcock, S.R. Pucher, A.G. Scopelianos, Poly[(amino acid es-ter)phosphazenes] synthesis, crystallinity, and hydrolytic sensitivity in solution and the solid state. Macromolecules 27 (5) (1994) 1071-1075. 

Suggest a mechanism for the general phosphazene synthesis mentioned above (5B.49). 

Phosphazene synthesis is conceptually rather simple, as illustrated below for a PI base. The P-N skeleton is first put together via a series of nucleophilic displacements (presumably of the 8 2-81 type) ... 

Montoneri, E., Gleria, M., Ricca, G., Pappalardo, G.C. (1989) New acid-polyfunctional water-soluble phosphazenes synthesis and spectroscopic characterization. Journal of Macromolecular Science Pure and Applied Chemistry, A26, 645-661. 

Properties. One of the characteristic properties of the polyphosphazene backbone is high chain dexibility which allows mobility of the chains even at quite low temperatures. Glass-transition temperatures down to —105° C are known with some alkoxy substituents. Symmetrically substituted alkoxy and aryloxy polymers often exhibit melting transitions if the substituents allow packing of the chains, but mixed-substituent polymers are amorphous. Thus the mixed substitution pattern is deUberately used for the synthesis of various phosphazene elastomers. On the other hand, as with many other flexible-chain polymers, glass-transition temperatures above 100°C can be obtained with bulky substituents on the phosphazene backbone. 

Scheme 14.5 Synthesis of a polymer with alternating phosphazene and oxathiazene units...

Table 1.1 Synthesis of aryl-vinyl epoxides by use of chiral sulfide 1 a phosphazene base.

Allcock HR. Qrganometallic and bioactive phosphazenes. J Polym Sci Polym Symp, 1983, 70, 71-77. Allcock HR. Poly(organophosphazenes) Synthesis, unique properties and applications. Makromol Chem... 

Abstract In this paper the synthesis, properties and applications of poly(organophos-phazenes) have been highlighted. Five different classes of macromolecules have been described, i.e. phosphazene fluoroelastomers, aryloxy-substituted polymeric flame-retardants, alkoxy-substituted phosphazene electric conductors, biomaterials and photo-inert and/or photo-active phosphazene derivatives. Perspectives of future developments in this field are briefly discussed. 

The synthesis of poly(organophosphazenes), POPs, is a research area that has involved a lot of effort in the past by many scientists active in the phosphazene domain. There are several important reasons for this, basically related to the high cost of the starting products [44] used to prepare POPs, to difficulties in carefully controlling the reactions involved in the preparative processes [38] and to the need for accurately predicting both molecular weight and molecular weight distribution of the POPs produced [38,45]. 

The synthesis of this material is one of the major processes in phosphazene chemistry, as proved by the unbelievably high number of papers and patents that have appeared since the beginning of the phosphazene history [ 10,58]. 

Based on the synthesis of polyphosphazenes and of diblock copolyphosp-hazenes by the living cationic polymerization of phosphoranimines [237,241], the triblock poly(phosphazene-ethylene oxide) copolymer XVIII was synthesized by Allcock [223]. 

The connection between hydrophobicity and tissue compatibility has been noted for classical organic polymers (19). A key feature of the polyphosphazene substitutive synthesis method is the ease with which the surface hydrophobicity or hydrophilicity can be fine-tuned by variations in the ratios of two or more different side groups. It can also be varied by chemical reactions carried out on the organo-phosphazene polymer molecules themselves or on the surfaces of the solid materials. 

A recent development has been the synthesis of bioerodible poly-phosphazenes that bear glyceryl side groups (35). The synthesis of these polymers requires a protection-deprotection sequence to reduce the functionality of the glycerol and prevent crosslinking. 

A mechanism for this reaction involving nucleophilic attack of the ylide on the cyanide group and formation of the P=N linkage via a four-centred intermediate was formulated. The structure of this phosphazene was confirmed by its synthesis from the vinyl azide, Ph(N3)C=CHPh, and triphenylphosphine. Phosphoranes stabilized by electron-withdrawing... 

The use of N3P3CI8 in the synthesis of amides has been described, although the fate of the phosphazene ring system was not clear ... 

An alternative method of synthesis of N3P3Cl6 has been developed recently, based on the reaction of tris (trimethylsilyl) amine and phosphorus pentachloride (40). This reaction either preferentially leads to the formation of N3P3C16 or to an N-silylated phosphoranimine intermediate C13P - NSiMe3, depending on the reaction conditions used. Thus the reaction between tris (trimethylsilylamine) and PC15 in methylene chloride at 40° C affords a mixture of cyclo and linear phosphazenes, which has been shown by an NMR analysis to contain up to 76% of N3P3C16 (Eq. 2). 

Reactions at the exocyclic position of cyclophosphazene derivatives represent a means for widely expanding the range of available phosphazenes. The synthesis of covalently bound cyclophosphazene heme complexes starts with N3P3 (OPh), -Cl which is converted to N3P3(OPh)5NMeCH2CH2CN. Following reduction of the... 

Macromolecular Substitution Route. The current surge in poly-phosphazene research Is mainly a result of the development in the mid 1960 s (2-4) of a substitutive route to the synthesis of organo phosphazene high polymers. Before that time, only a sporadic interest in the subject existed because the known polymers, cross linked poly(dihalophosphazenes), (1,5) were insoluble and hydrolytically unstable. 

With this synthetic and molecular structural diversity, polyphosphazene chemistry has developed into a field that rivals many areas of organic polymer chemistry with respect to the tailored synthesis of polymers for specific experimental or technological uses. Indeed, hybrid systems are also available in which organic polymers bear phosphazene units as side groups. This is discussed in another Chapter. 

An overview of the synthesis and characterization of a unique class of polymers with a phosphorus-nitrogen backbone Is presented, with a focus on poly(dichloro-phosphazene) as a common Intermediate for a wide variety of poly(organophosphazenes). Melt and solution polymerization techniques are Illustrated, Including the role of catalysts. The elucidation of chain structure and molecular weight by various dilute solution techniques Is considered. Factors which determine the properties of polymers derived from poly(dichlorophos-phazene) are discussed, with an emphasis on the role that the organic substituent can play In determining the final properties. 

The true value of the chloropolymer (I) lies in its use as an intermediate for the synthesis of a wide variety of polytorgano-phosphazenes) as shown in Figure 1. The nature and size of the substituent attached to the phosphorus plays a dominant roll in determining the properties of the polyphosphazene. Homopolymers prepared from I, in which the R groups are the same or, if different, similar in molecular size, tend to be semi-crystalline thermoplastics. If two or more different substituents are introduced, the resulting polymers are generally amorphous elastomers. (See Figure 1.)... 

---