FORMATION DE P-TRICHLORO-N-DICHLOROPHOSPHORYLE MONOPHOSPHAZENE PAR ACTION D'O-NUCLEOPHILES SUR LE CHLORURE ET L'HEXACHLOROPHOSPHATE D'HEXACHLORODIPHOSPHAZONIUM NOUVELLE PREPARATION DE BISDICHLOROPHOSPHORYLIMIDE PUR

Abstract

A ³¹P-NMR investigation has been made of the action of (Cl₃P—N—PCl₃)⁺Cl⁻ (I) and (Cl₃P—N—PCl₃)⁺ PC⁻ ₆ (II) first, on bisdichlorophosphorylimide HN(POCl₂)₂ (III) and then on methanol and ethanol in dioxane at room temperature.

With (I) the main product, which can represent up to 100% total phosphorus, is Cl₃P[dbnd]N—POCl₂ (IV); with (II) it also forms POCl₃. In these reactions the intermediate (Cl₃P—N—PCl₃)⁺ (N(POCl₂)₂)⁻ (V), which changes in a few hours into (IV), can be identified. The secondary products in weak proportion, are the monoalcoyl derivatives of (IV) and POCl₃. If the nucleophile is in excess HN(POCl₂)₂ is obtained.

The preparation of HN(POCl₂)₂, which is only slightly soluble in nitromethane, is carried out by a simple hydrolysis of Cl₃P=N—POCl₂ (IV) in this solvent with less than a stoichiometric quantity of liquid water. After filtering and washing, a pure product is obtained directly.

Key Words:

• Phosphazenes
• hexachlorodiphosphazonium salts
• reactivity
• bisdichlorophosphorylimide
• alcohols
• NMR