Molecules 2013, 18(11), 13940-13956; doi:10.3390/molecules181113940
Article

Synthesis of a Versatile Building Block Combining Cyclen-derivative DO3A with a Polyamine via a Rigid Spacer

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Received: 8 October 2013; in revised form: 5 November 2013 / Accepted: 6 November 2013 / Published: 12 November 2013
(This article belongs to the Section Organic Synthesis)
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract: The five-step synthesis of a polydentate building block combining a cyclen-based macrocycle (DO3A) with N-(2-aminoethyl)propane-1,3-diamine, which are linked through the xylylen moiety as a rigid C-spacer is described. These two molecular parts were coupled by subsequent bromine atom substitution in 1,4-bis(bromomethyl)benzene. First, N-(2-aminoethyl)propane-1,3-diamine was protected by phthaloyl moieties and then it was reacted with 1,4-bis(bromomethyl)benzene to form (2-phthalimidoethyl)(3-phthalimido-prop-1-yl)(4-bromomethylbenzyl)amine (2). This compound underwent a substitution reaction with DO3A in the form of its tert-butyl esters leading to the intermediate 1-{4-[(2-phthalimidoethyl)(3-phthalimidoprop-1-yl)aminomethyl]phenylmethyl}-4,7,10-tris(t-butoxy-carbonylmethyl)-1,4,7,10-tetraazacyclododecane (3). The phthaloyl as well as the t-butyl protecting groups were removed in the next two reaction steps to form the final product 1-{4-[(2-aminoethyl)(3-aminoprop-1-yl)aminomethyl]phenylmethyl}-4,7,10-tris(carboxy-methyl)-1,4,7,10-tetraazacyclododecane (5). The intermediates 14 as well as the final product 5 were characterized by elemental analysis, mass spectrometry, and multinuclear (1H and 13C) and two-dimensional NMR spectroscopy. The final product 5 could serve as a potential building block in subsequent syntheses of binuclear complexes of lanthanides and/or transition metals.
Keywords: synthesis; DO3A macrocycle; building block; NMR spectroscopy; mass spectrometry
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MDPI and ACS Style

Drahoš, B.; Trávníček, Z. Synthesis of a Versatile Building Block Combining Cyclen-derivative DO3A with a Polyamine via a Rigid Spacer. Molecules 2013, 18, 13940-13956.

AMA Style

Drahoš B, Trávníček Z. Synthesis of a Versatile Building Block Combining Cyclen-derivative DO3A with a Polyamine via a Rigid Spacer. Molecules. 2013; 18(11):13940-13956.

Chicago/Turabian Style

Drahoš, Bohuslav; Trávníček, Zdeněk. 2013. "Synthesis of a Versatile Building Block Combining Cyclen-derivative DO3A with a Polyamine via a Rigid Spacer." Molecules 18, no. 11: 13940-13956.

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