Trimeric phosphonitrilic chloride

Figure 1. Scheme showing the polymerization of the trimeric phosphonitrilic chloride to poly(dichlorophosphazene) and its subsequent substitution with the sodium salts of alcohols or phenols... 

TRIMERIC PHOSPHONITRILE CHLORIDE AND TETRAMERIC PHOSPHONITRILE CHLORIDE... 

In a 1-1. flask fitted with a stirrer is placed a solution of 60 g. of trimeric phosphonitrile chloride in 240 ml. of diox-ane and a solution of 300 g. of potassium acetate in 300 ml. of water. The temperature is held at 45 to 55°, cooling at first with a cold-water bath, later heating with a heating... 

The hydrolysis of trimeric phosphonitrile chloride dissolved in ether and shaken with aqueous sodium acetate solution was described by Stokes.1 It is slow and uncertain, however, and the substitution of dioxane for ether, as practiced by de Fiequelmont in related preparations,2 is preferred. 

Chlorofunctional triazadiphosphinines range between 1,3,5-triazine and chloro-cyclotriphosphazenes (trimeric phosphonitrilic chlorides). They give substitution reactions and thermal polymerization like the latter. The tetrachloro derivatives may be prepared in a [5 + 1] cyclocondensation from N, N-bis(trichlorophosphoranylidene)amidinium hexachloroantimon-ates and ammonium chloride or in a [3 + 3] cyclocondensation from ami-... 

Phosphonitrilic chloride (trimer) (bexachlorocyclotriphosphazine) [940-71-6] M 347J, m 112.8 , 113-114°. Purified by zone melting, by crystallisation from pet.ether, n-hexane or benzene, and by sublimation, [van der Huizen et al. J Chem Soc, Dalton Trans 1311 1986 Meirovitch et al. J Phys Chem 88 1522 1984 Alcock et al. J Am Chem Soc 106 5561 1984 Winter and van de Grampel J Chem Soc, Dalton Trans 1269 1986.]... 

Phosphonitrilic chloride PCI5+NH4CI atl50°C, or by heating cyclic trimer Cl — i>=N— 1 Rubberlike, crystallizes on stretching. Swells in benzene... 

AMIDO(PHOSPHONITRILIC CHLORIDE-CYCLIC TRIMER) AND 1,1 -DIAMIDO(PHOSPHONITRILIC CHLORIDE-CYCLIC TRIMER)... 

Only three amido derivatives of phosphonitrilic chloride-cyclic trimer have been described, namely, the compounds... 

C.) The solid remaining after filtration of the cooled suspension is recrystallized from diethyl ether by cooling the saturated solution to — 70°C. Yield, based upon phosphonitrilic chloride—cyclic trimer, is 80-95 g. (60-72%) m.p., 163-165°C. Anal. Calcd. for N3P3C14 (NH2 )2 N, 22.68 H, 1.31. Found N, 22.94 H, 1.35. The checkers report equally good results, working on one-third of the above scale. 

Amido (phosphonitrilic chloride—cyclic trimer) is a white crystalline, slightly hygroscopic solid, which melts at 138-139°C. and dissolves in both 1,4-dioxane and carbon tetrachloride. Slow... 

Trimeric and tetrameric phosphonitrile chlorides are among the products formed in the reaction of phosphorus-... 

Phosphonitrile chloride, trimeric and tetrameric, 6 94 Phosphonium iodide, 2 141, 143 all-glass apparatus for preparation of, 6 91... 

The compound 1,1-NsPsF4(CsHc)i can be prepared by the reaction between (monophenyl)phosphonitrile fluoride trimer and benzene in the presence of anhydrous aluminum chloride and triethylamine.2 In the absence of triethylamine, the product is contaminated with difficultly separable biphenyl. Triethylamine also improves the conversion of phosphonitrile chloride trimer to the geminally substituted diphenyl derivative6 by the Friedel-Crafts procedure.7 The Friedel-Crafts reaction can be used also for the preparation of the geminally substituted... 

The cyclic sulfanuric chlorides, (NS0C1) , are of interest because they are isoelectronic with the cyclic phosphonitrilic chlorides, (NPCl2)n- Although the formation of a variety of substances with n = 3 or more appears reasonable, only the cyclic trimers have been isolated.1 At least three, apparently conformational, isomers of composition (NSOCl)3 have been... 

Hexaethoxycyclotriphosphazatriene may be prepared by the slow addition of dry ethanol to a cold, stirred solution of hexachlorocyclotriphosphazatriene (1,3,5,2,4,6-triazatri-phosphorine 2,2,4,4,6,6-hexachloride phosphonitrile chloride, cyclic trimer) in dry pyridine. The reaction mixture is worked up by the addition of an excess of dry diethyl ether and filtration of the precipitated pyridinium hydrochloride. The solvents are then removed from the washed and dried solution and the product is purified by vacuum distillation. 

The question of whether the phosphonitrilic chlorides have cyclic or linear structures has been frequently discussed in the literature. The structural evidence will be considered in Section lY, where it will be seen that the cyclic formulation is established beyond doubt for the trimer and tetramer, and is highly probable for the higher soluble polymers it will meanwhile be assumed for all compounds of formula (PNX2) . For reasons considered in Section II, C the petrol-insoluble fraction (PNCUln PCls is believed to consist of a mixture of linear polymers. The two series are related, in that the linear compounds of low molecular weight are intermediates in the formation of the cyclics by the ammonolysis of phosphorus pentachloride. 

Trimeric phosphonitrilic azide has been prepared (57) from the trimeric chloride and sodium azide in solution in acetone. 

The reactions of primary and secondary amines with the phosphonitrilic chlorides have been studied by several investigators. Complete aminolysis is difficult to attain (see p. 127 in ref. 5), though fully substituted derivatives of the trimer and tetramer have been reported. 

Ultraviolet light has no effect on the phosphonitrilic chlorides themselves. Dishon and Hirshberg S2) found that solutions of the trimeric and tetrameric chlorides in hydrocarbon solvents became brown on irradiation with light from a mercury arc, and were able to isolate from the product distillable phenol and decahydronaphthyl derivatives, the formation of whii U su ests radical attack. 

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