Synthesis of Ester Derivatives of 1,4,7-Triazacyclononane-1,4,7-tris(methylenephosphonic Acid) and 1,4,7-Triazacyclononane-1,4,7-tris(methyleneethylphosphinic Acid)

István Lázár; A. Dean Sherry

doi:10.1055/s-1995-3923

Synthesis 1995; 1995(4): 453-457
DOI: 10.1055/s-1995-3923

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Synthesis of Ester Derivatives of 1,4,7-Triazacyclononane-1,4,7-tris(methylenephosphonic Acid) and 1,4,7-Triazacyclononane-1,4,7-tris(methyleneethylphosphinic Acid)

István Lázár¹ , A. Dean Sherry²

¹Department of Inorganic and Analytical Chemistry, Lajos Kossuth University, Debrecen-10, P.O. Box 21, H-4010, Hungary
²Department of Chemistry, The University of Texas at Dallas, P.O. Box 830688, Richardson, Texas 75083-0688, USA

Abstract

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Two methods have been developed for the synthesis of new 1,4,7-triazacyclononanetris(methylenephosphonic acid) (3-6, 8-11) and -tris(methyleneethylphosphinic acid) (7, 12) ester derivatives. The first procedure includes the synthesis of 2 in anhydrous THF which can then be used as a useful synthetic intermediate for several new derivatives of 1,4,7-triazacyclononane (1). In the second procedure, compound 1 and dialkyl phosphite or ethyl ethylphosphinate are reacted with paraformaldehyde in refluxing benzene yielding the corresponding esters in good to excellent yield. New macrocyclic complexing agents 8-12 have been prepared by either basic (8-11) or acidic (12) hydrolysis of the corresponding ester derivatives, or directly from the starting macrocycle 12. Side reactions decreasing the yield and purity of the products are also discussed.

macrocycles - 1,4,7-triazacyclononane - Mannich reaction - phosphorus - NMR probes

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