Heteroatom Chemistry Volume 14, Number 2, 2003 Arylation Reaction of N -Dichlorophosphoryl- P-trichlorophosphazene M. Arslan, 1 F. Aslan, 2 and A. I. Ozturk 2 1 Chemistry Department, Firat University, TR-23169 Elazig, Turkey 2 Chemistry Department, Harran University, TR-63100 Sanliurfa, Turkey Received 4 July 2002 ABSTRACT: The reactions of N-dichlorophosphoryl- P-trichlorophosphazene (Cl 3 P N POCl 2 ) with pheny- lmagnesium chloride, o-tolylmagnesium chloride, p- tolylmagnesium chloride, p-chlorophenylmagnesium chloride, 2-mesitylmagnesium bromide, and 2-thienyl lithium were studied. The resulting pentaaryl phos- phazenes R 3 P N P(O)R 2 were separated by using column chromatography, their structures were de- fined by IR, elemental analysis, 1 H, 13 C, 31 P NMR, and mass spectroscopy. C  2003 Wiley Periodicals, Inc. Heteroatom Chem 14:138–143, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10114 INTRODUCTION Only a few short-chain phosphazenes have been characterized in detail [1–9]. The reactions of compound 1 with amines and alcohols have been reviewed [10,11]. The structures of 1 [12] and some of its derivatives, such as its pen- taamide 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 geminal- bis(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-methyl- phenoxide) Cl(OC 6 H 2 Bu t -2,6-Me-4) 2 P N P(O)Cl 2 Correspondence to: M. Arslan; e-mail: marslan07@yahoo.com. Contract grant sponsor: Scientific and Technical Research Council of Turkey. Contract grant number: TBAG-1611. c  2003 Wiley Periodicals, Inc. 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 [17–24]. Three routes can accomplish the synthesis of phosphazenes that contain alkyl or aryl groups bonded directly to phosphorus by direct synthe- sis, Friedel–Craft reactions, and the interaction of organometallic compounds with halophosphazenes [1]. The reactions between halogenophosphazenes and main group organometallic reagents have been studied during last 30 years [2,25], but these re- actions can be complex, and some of the earlier work in this area has had to be reinterpreted as the degree of complexity has been recognized [26]. Several transition-metal-containing cyclic phosp- hazenes have been synthesized [27]. In the synthe- sis of alkyl- and aryl-substituted phosphazenes, a halophosphazene is reacted with an organolithium or Grignard reagent [28–33]. Although there are many publications about cyclic, polymeric alkyl-, or arylphosphazenes [34–40], the synthesis of linear alkyl-substituted phosphazenes has been performed with only limited success [41,42]. Here we report the reactions of Cl 3 P N P(O)Cl 2 (1) with aryllithium and aryl-Grignard reagents. Pen- tasubstituted phosphazenes were obtained as major products. RESULTS AND DISCUSSION The reaction of 1 with 10 equiv. of phenylmag- nesium chloride, o-tolylmagnesium chloride, p-tolyl- magnesium chloride, p-chlorophenylmagnesium 138