A series of bis(2-arylaminoethyl)amines was prepared by hydrolysis of the corresponding bicyclic phosphoric triamides, followed in some cases by further functionalization.Ammonia and amines represent one of the most common types of F-donors ligands in coordination chemistry, and the polyamines with the typically 1,2-or 1,3-location of the amino groups are widely used as polydentate chelating ligand structures. 1 Bis-(2-aminoethyl)amine and its derivatives can coordinate a metal via two five membered chelate rings and should, according to their steric requirements, 2 show selectivity towards fairly large metal ions. The complexation of Cu 2+ with 3,6,9-triazaundecane and its 1,11-disubstituted derivatives has been studied by potentiometric and spectrophotometric titrations. 3 The terdentate ligand derived from 3,9-diethyl-3,6,9-triazaundecane was used in a study of complexes of metals of the Ti and V triads. 4The obvious way to ethyleneamines and higher polyamines is to react ethylene dihalide with ammonia or with amines. The reaction was studied in late 1860's by Hofmann, 5 and the complexity of the reaction and its product was soon acknowledged. The reaction was reinvestigated by Mann, 6 who demonstrated that the parent triamine, bis(2-aminoethyl)amine ("diethylenetriamine") can be obtained in pure state as a hydrochloric acid salt only indirectly, via the Gabriel's method. The N,N¢-diaryl substituted "diethylenetriamine", Ar-NH-CH 2 CH 2 -NH-CH 2 CH 2 -NH-Ar 1, is an interesting example of that parent system because of the possibility of wide variations of its electronic and steric effects that may be achieved by introducing substituents to the aromatic groups, as well as at the nitrogen atoms of the 1,4,7-triazaheptane skeleton. The N,N¢-diphenyl derivative 1a (Ar = Ph), although a simple compound, is difficult to prepare. The patent literature reports formation of small quantities of 1a, together with other amines, in the reduction of the nitrile of N-phenylglycine; the mixture of amines can be used as a vulcanization accelerator, antioxidant, or as an insect poison. 7 Compound 1a is also formed as a side product (35%) together with N-phenylethylenediamine (65%) in the reaction of N-(2-chloroethyl)aniline with liquid NH 3 . 8 Prelog and Driza have demonstrated long ago 9 that the reaction between bis(2-chloroethyl)amine and aniline is not a practical route to 1a, since the major product of the reaction is N-phenylpiperazine (Scheme 1). We have repeated Prelog's experiment by reacting bis(2-chloroethyl)ammonium chloride with 5.1 mol equivalents of aniline in boiling toluene, and analyzsing the reaction product by high-resolution 1 H NMR spectroscopy. After neutralization, the reaction mixture consisted of N-phenylpiperazine, some 1a, and aniline; the integration of the 1 H NMR signals indicated the preference for the intermediate monosubstitution product (Scheme 1) to undergo intramolecular cyclization (piperazine formation) rather than the second substitution (formation of 1a) in a ratio of approximately 7:1....