Under solvent-free reaction conditions and in the presence of solid LiClO4 a novel and mild protocol for the one-pot, three-component synthesis of primary alpha-amino phosphonates from an aldehyde, hexamethyldisilazane and a trialkyl phosphite is described giving high yields and having short reaction times. The same products are obtained in very low yields, when the three-component reaction is carried out under microwave irradiation and in the absence of solid LiClO4. Examples of some prepared 1-aryl-N,N'-bis(arylidene)inethanediamines are also described. (C) 2004 Elsevier Ltd. All rights reserved.