TriAmide, phosphoryl

Phosphoryl triamide is formed when ammonia reacts with phosphoryl trichloride in chloroform under good cooling 1 

Separation of the reaction products is accomplished by reaction of ammonium chloride with diethyl ami no to form ammonia and diethylammonium chloride, which is soluble in chloroform  

The remaining unchanged, chloroform-insoluble phosphoryl triamide is readily recrystallized from methanol.2 

While the mixture is stirred well, a steady stream of ammonia maintained, and the temperature held at —15°, the phosphoryl trichloride solution is allowed to drip into the ammonia-saturated chloroform over a period of 2 hours. The stream of ammonia is maintained for another hour. Then the cooling mixture is removed and the reaction mixture may remain overnight. The precipitate formed is sucked off rapidly by means of a Buchner funnel, washed with dry chloroform, and dried under vacuum. The yield is approximately 110 g. 

The compound is next placed in a round-bottomed flask fitted with a reflux condenser, mixed with 225 ml. of dry chloroform, and 160 g. (230 ml.) of diethylamine, and the mixture kept at 60° for 9 hours. A higher temperature is to be avoided because of decomposition. Then 200 ml. of chloroform is added and the remaining oxyphosphorus triamide filtered off. It is washed with dry chloroform until the chloride reactions in the product and wash solution are 

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H. Schiff claimed to have prepared PO(NH2)3, or phosphoryl triamide, by slowly leading a current of dry ammonia into cold phosphoryl chloride until the mass was quite sat. The ammonium chloride was washed from the product of the action with cold or warm water, and phosphoric triamide remained as a snow-white powder. H. Schiff claimed that the compound is scarcely attacked by boiling water, an aq. soln. of potassium hydroxide, or dil. acids but that it is slowly attacked by cone, acids. When fused with potassium hydroxide, ammonium and potassium phosphates are formed and when heated out of contact with air, ammonia, and phosphoryl nitrile are produced PO(NH2)3=PON-fi2NH3. J. H. Gladstone, A. Mente, and H. N. Stokes failed to confirm the preparation of H. Schiff s triphosphoramide. According to J. H. Gladstone, the third atom of chlorine cannot be replaced by an amido-group at any temp, below that at which further decomposition occurs (300°). The product of the action of ammonia on phosphoryl chloride is a mixture of ammonium salts of amido- and imido-tetra-phosphoric acids. 

Phosphoryl triamide forms colorless crystals, probably monoclinic. It is readily soluble in methanol, very soluble in water, but unstable in this solution as it is transformed into orthophosphate via amidophosphates it is insoluble in ethanol. When heated with sodium hydroxide diamido-phosphate is formed. 

When hydrogen chloride is passed into a suspension of phosphoryl triamide in ether at —15° imidodiphos-phoric acid tetramide, (NH2)2P(0)—NH—P(0)(NH2)2, is formed at +30° diimidotriphosphoric pentamide is formed. Both these compounds are formed simultaneously when phosphoryl triamide in toluene is heated to 120°. After some weeks in humid air phosphoryl triamide forms ammonium hydrogen monoamidophosphate. For storage the compound must be sealed off in a glass tube. With... 

Thiophosphoryl triamide is prepared in a manner analogous to that of phosphoryl triamide, involving the reaction of ammonia with thiophosphoryl trichloride in chloroform while cooling 1... 

Diimidotriphosphoric pentamide, formation of, from phosphoryl triamide, 6 110... 

Imidodiphosphoric acid tetramide, formation of, from phosphoryl triamide, 6 110, llln. Iodination apparatus, for preparation of chromium(III) iodide, 6 128... 

Triamidophosphorlc Acid or Phosphoryl Triamide, PO(NH2)3, was prepared by passing dry ammonia into dry phosphoryl chloride. After washing out the ammonium chloride, an insoluble white powder was left, which was scarcely affected by dilute acids or alkalies, but was decomposed by fusion with potash.3... 

I. Thiophosphoryl triamide is obtained similarly to phosphoryl triamide (see p. 584) via reaction of NH3 and PSCI3 in chloroform solution. The reaction flask must be well cooled (Klement and Koch) ... 

Phosphoryl chloride is reduced by carbon to the trichloride (4.206), and with liquid ammonia, phosphoryl triamide is obtained (7.48). 

Amorphous polymeric materials with composition (PON) and (PSN) can be obtained from reactions of NHj with POCI3 and PSCI3, respectively. With more limited reactions, phosphoryl triamide or thiophosphoryl triamide (7.48) can be made. These compounds are colourless crystalline solids which are soluble in water, but the action of heat will eventually transform them into (PON) and (PSN) . The polymeric oxynitride can be made crystalline by heating to 700°C under pressure. 

Phosphoryl trihydrazide, OP(NH-NH2)3, can be made by reacting hydrazine with phosphoryl chloride in anhydrous ether at -12°C (7.52). The compound forms colourless hygroscopic needles which are more stable than phosphoryl triamide, OP(NH2)3, but in aqueous solution, it slowly decomposes to give hydrazine, N2H4. 

Phosphoryl triamide, PO(NH2)3, can be made by the direct reaction of liquid ammonia with phosphoryl chloride (7.48), or with triphenyl phosphate (7.64). It forms colourless needles which are very soluble in water, but insoluble in most organic solvents. Prolonged heating results in transformation into polymeric material. Dilute acid hydrolysis or atmospheric moisture will yield mono-ammonium phosphoramidate, while with dilute NaOH, sodium phosphorodiamidate is formed (7.65)... 

If dry HCl is passed into a suspension of PO(NH2)3 in ether at -10°C, the corresponding imido compound, imido diphosphoramide is prodnced (7.76). This compound is also produced, along with other more highly condensed imidophosphates, by simply heating dry phosphoryl triamide. The componnd evolves NH3 on heating to 70°C. 

A highly insoluble and inert polyphosphimate is obtained by heating phosphoryl triamide at... 

Phosphoryl triamides, (R2N)3PO, are hydrolysed in warm acid media but they can be precipitated by alkali from cold concentrated HCl solutions without breaking the P-N linkages. Phosphordiamidic chlorides are hydrolysed by water or acids, but they are much more stable in alkaline media and limited water can result in condensation (7.112) (Figure 7.3). 

The lUPAG 1957 rules use these radicals also for amides, giving S02(NH2)2 sulphonyl diamide and PO (NH2)s phosphoryl triamide. As alternatives they give sulphuric diamide and phosphoric triamide. For the partial amides they put forward -amidic add names, and as an alternative the use of co-ordination nomenclature for example, NH2 S03H sulphamidic... 

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