Selective Protection of 1,4,8,11-Tetraazacyclotetradecane (Cyclam) in Position 1,4 with the Phosphonothioyl Group and Synthesis of a Cyclam-1,4-bis(methylphosphonic Acid). Crystal Structures of Several Cyclic Phosphonothioamides

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Title:Selective Protection of 1,4,8,11-Tetraazacyclotetradecane (Cyclam) in Position 1,4 with the Phosphonothioyl Group and Synthesis of a Cyclam-1,4-bis(methylphosphonic Acid). Crystal Structures of Several Cyclic Phosphonothioamides
Creators:
Vitha, Tomáš
Kotek, Jan
Rudovský, Jakub
Kubíček, Vojtěch
Císařová, Ivana
Hermann, Petr
Lukeš, Ivan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 71, 3, pp. 337-367
Uncontrolled Keywords:Cyclam <i>cis</i>-protection, Phosphonate ligands, Aminophosphonic acids, TETP, Cyclam, Crystal structure determination, Azacycle, Cyclen, Macrocyclic ligands, Thiophosphonic amides, Radiopharmaceuticals, Azacrown

Abstract

A new cyclam-based ligand, 1,4,8,11-tetraazacyclotetradecane-1,4-bis(methylphosphonic acid) (1,4-H<sub>4</sub>te2p), was synthesized. Cyclam was protected by the reaction with PhP(S)Cl<sub>2</sub> to form exclusively five-membered cyclic phenylphosphonothioic diamide <strong>2</strong> in a moderate yield. The solid-state structures of <strong>2</strong> and several by-products were determined. Compound <strong>2</strong> was isolated as two stable conformers differing in a mutual position of benzene ring and sulfur atom with respect to the cyclam ring. Compound <strong>2</strong> was used for the synthesis of 1,4-dibenzylcyclam. However, the deprotection of the thiophosphoryl-protected bis(methylphosphonate diester) with aqueous HCl under non-optimized conditions led to a mixture of cyclam derivatives differently substituted with methylphosphonic acid groups. The crystal structures of the target product, 1,4-H<sub>4</sub>te2p, and also 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetrakis(methylphosphonic acid) (H<sub>8</sub>tetp) were determined. A similar reaction with cyclen (1,4,7,10-tetraazacyclododecane) led only to hardly purifiable mixtures. <p>

Title:Selective Protection of 1,4,8,11-Tetraazacyclotetradecane (Cyclam) in Position 1,4 with the Phosphonothioyl Group and Synthesis of a Cyclam-1,4-bis(methylphosphonic Acid). Crystal Structures of Several Cyclic Phosphonothioamides
Creators:
Vitha, Tomáš
Kotek, Jan
Rudovský, Jakub
Kubíček, Vojtěch
Císařová, Ivana
Hermann, Petr
Lukeš, Ivan
Uncontrolled Keywords:Cyclam <i>cis</i>-protection, Phosphonate ligands, Aminophosphonic acids, TETP, Cyclam, Crystal structure determination, Azacycle, Cyclen, Macrocyclic ligands, Thiophosphonic amides, Radiopharmaceuticals, Azacrown
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:71
Number:3
Page Range:pp. 337-367
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20060337UNSPECIFIED
ID Code:2483
Item Type:Article
Deposited On:06 Feb 2009 17:19
Last Modified:06 Feb 2009 16:19

Citation

Vitha, Tomáš; Kotek, Jan; Rudovský, Jakub; Kubíček, Vojtěch; Císařová, Ivana; Hermann, Petr; Lukeš, Ivan (2006) Selective Protection of 1,4,8,11-Tetraazacyclotetradecane (Cyclam) in Position 1,4 with the Phosphonothioyl Group and Synthesis of a Cyclam-1,4-bis(methylphosphonic Acid). Crystal Structures of Several Cyclic Phosphonothioamides. Collection of Czechoslovak Chemical Communications, 71 (3). pp. 337-367. ISSN 0010-0765

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