A New Route to the Phosphazene Polymerization Precursors, Cl₃PNSiMe₃ and (NPCl₂)₃

Abstract

An improved synthesis of the phosphazene polymerization precursors, hexachlorocyclotriphosphazene, (NPCl2)3 (1), and Cl3PNSiMe3 (2) is reported. The addition of PCl5 to N(SiMe3)3 in methylene chloride at 40 °C produced a mixture of phosphazenes which contained 76% of 1. However, the addition of N(SiMe3)3 to PCl5 in methylene chloride at 0 °C, followed by the addition of hexane, provided 2 in 40% yield. The mechanism of the reaction is discussed.

A direct synthesis of Сl3P NSiMe3 from PCl5 and hexamethyldisilazane

“…Initially the synthesis of phosphoranimine was carried out as reported [13], using dichloromethane as a solvent. In contrast to the preparation of phosphoranimine via LiN(SiMe 3 ) 2 and PCl 5 interaction, the ambient temperature reaction of equimolar amounts of HMDS and PCl 5 or with an excess of the latter leads to the predominant formation of an intermediate Cl 3 P=NH at the first stage of the process.…”

“…All reactions were carried out under inert atmosphere of dry nitrogen using standard Schlenk techniquies. 1 H, 13 C and 31 P NMR spectra were recorded on a Bruker CXP-200 spectrometer operating at frequencies of 200, 50.3 and 81 MHz, respectively. The spectra were recorded in CDCl 3 and reported in parts per million (δ) relative to residual solvent signal for 1H (7.26 ppm) and 31 C NMR (77.0 ppm) spectra, and 85% H 3 PO 4 (0.0 ppm) as external standard for 31 P NMR spectra.…”

“…Later Allcock and co-workers have reported an alternative synthesis of Cl 3 P=NSiMe 3 from PCl 5 and N(SiMe 3 ) 3 with no formation of byproduct, chloramine, occurred [13]. The yield of the product after purification is up to 40%.…”

Arylation reaction of N‐dichlorophosphoryl‐P‐trichlorophosphazene

“…The structures of 1 [12] and some of its derivatives, such as its pentaamide derivative (PhNH) 3 P N P(O)(NHPh) 2 [13], its geminal-bis(diisopyropylamino) derivative Cl[NCH(CH 3 ) 2 ] 2 P N P(O)Cl 2 [14], and its geminalbis(2,4,6-tert-butylphenoxide) Cl(OC 6 H 2 Bu t -2,4,6) 2 -P N P(O)Cl 2 and bis(2,6-di-tert-butyl-4-methylphenoxide) Cl(OC 6 H 2 Bu t -2,6-Me-4) 2 P N P(O)Cl 2 derivatives [15] have been reported. These molecules can be used as structural models for the inorganic polymers with a large range of properties [2,16] and applications [17][18][19][20][21][22][23][24]. Three routes can accomplish the synthesis of phosphazenes that contain alkyl or aryl groups bonded directly to phosphorus by direct synthesis, Friedel-Craft reactions, and the interaction of organometallic compounds with halophosphazenes [1].…”

The reaction OF N‐dichlorophosphoryl‐ P‐trichlorophosphazene with alkyl grignard reagents

“…The partial aminolysis and alcoholysis of 1 with methylamine and tertbutylamine [16], diisopyropylamine [17], o-dichloro and o-dimethylphenol [18], 2,4,6-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol [19], and allyl alcohol [20] have been reported. These molecules can be used as structural models for phosphazene polymers with a large range of properties [2,21] and applications [22][23][24][25][26][27][28][29].…”