The addition reaction between the P‐H bond of tetraoxyspirophosphoranes 1‐2 and long‐chain imines 3a‐h (decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and oleyl imines) occurs instantaneously at room temperature. It is diastereoselective, and quantitatively leads to the corresponding (α‐aminoalkyl)spirophosphoranes 4a‐h and 5e. The influence of the pentacoordinated phosphorus atom on the stereoselectivity of the Pudovik reaction might be attributed to the involvement of the rigid spirophosphoranide (PV) intermediate in the addition reaction. Selective and one‐pot hydrolysis of these P‐C bond spirophosphoranes readily proceeds either at room temperature in the presence of moist solvents to give the corresponding carboxyalkyl (α‐aminoalkyl)phosphonic acid monoesters 6a‐h and 7e, or the reaction may be carried out in the presence of 20% aqueous hydrochloric acid under reflux, to afford the free (α‐aminoalkyl)phosphonic acid amphiphiles 8a‐h in high yields. In contrast to their sodium salts, these single‐ and double‐chained free and monoester phosphonic acid amphiphiles exist as zwitterions and are not soluble in water.

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Molecular modelling of hexachlorocyclotriphosphazene, N3P3C16, was achieved by using softwares produced by Biosym Technologies. The CVFF (Consistent Valence ForceField) and ESFF (Extended Standard ForceField) parameters for all atoms including the endocyclic P ones were tuned using results from X-ray analyses and they appeared to be quite convenient for reproducing geometries and conformations of many small phosphorus-nitrogen compounds belonging to the cyclophosphazenic series.