New Heavy Metal Ion‐Selective Macrocyclic Ligands with Nitrogen and Sulfur Donor Atoms and their Extractant Properties

The synthesis and characterization of 22-membered diazapentathia macrocycles and investigation of their ion extraction capability from aqueous media

“…The preparation of two ligands containing nitrogen and sulfur donor atoms (5) and (6) [1,7,10,13,19,4,16] pentathiadiazacyclodocosine (6) (70% yield) was obtained from the precursor a-bisamide macrocyclic compound (5) by using sodium boronhydride-boron trifluoride ethyl etherate in dry THF at 0-5°C under argon atmosphere. Analytical and spectroscopic data of compound (6) clearly confirmed the success of the reduction reaction.…”

“…Our previous work has focused on the use of the N 2 O 2 S 2 macrocycles with aromatic moieties, diazatetrathia and diazapenthia mixed donor for the transfer of various metal ions from the aqueous phase into the organic phase in liquid-liquid extraction systems [8][9][10]. In the present work we report the synthesis of two new N 2 S 5 mixed-donor macrocycles and study their selectivity for metal ion extraction.…”

“…The white crude product was recrystallized from acetonitrile to give white crystals. [1,7,10,13,19,4,16] pentathiadiaza-cyclodocosine-6,16(7H,17H)-dione (5) A solution of 2,2¢-dithioethanthiol (4) (0.695 g, 4.51 mmol) in dry DMF (75 ml) in a dropping funnel and a solution of (3) (2.0 g, 4.51 mmol) in dry DMF (75 ml) in a dropping funnel were added simultaneously under stirring and dry argon gas to dry DMF (50 ml) containing anhydrous sodium carbonate (1.91 g, 18 mmol) over 1.5 h at room temperature with continuous stirring. After addition was completed, reaction mixture was stirred at room temperature for another 2 h. The reaction was monitored by thin layer chromatography [pentane-ethyl acetate (6:4)].…”

“…The mass spectrum of compound (3) displayed the expected molecular ion peak at m/z = 444 [M + 1] + in the mass spectrum obtained using the (EI) MS technique. The reaction of N-[2-({3-[(2-aminophenyl)thio]propyl}thio)phenyl]-2-chloroacetamide (3) with 2,2¢-dithioethanethiol (4), 4 folds excess of anhydrous K 2 CO 3 in DMF at room temperature under argon atmosphere afforded 9,10,12,13,24,25-hexahydro-5H, 15H,23H-dibenzo[b,q][1,7,10,13,19,4,16]pentathiadiazacyclodocosine-6,16(7H,17H)-dione (5) in 93% yield. The i.r.…”

Synthesis and metal ion binding properties of thiaaza crown macrocycles

“…Especially, mercury is considered a highly dangerous element because of its toxic properties. Many mercury compounds are produced in industrial processes and disposed off to the environment.In the previous studies, we have investigated solvent extraction properties of some macrocyclic ionophores containing diazapentaoxa, diazatetrathia, and diazapentathia mixed donor atoms for heavy metals [9][10][11]. In this work, we have been interested in the design and synthesis of two novel macrocyclic ligands with diazatetrathia mixed donor atoms, and also solvent extraction properties for the transition metal cations such as Ag + , Hg 2+ , Cd 2+ , Zn 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Co 2+ , and Pb 2+ have been investigated.…”