Tetrathia-14-crown

Although the first all-sulfur macrocycles were prepared many years ago " the first systematic study of such compounds was initiated by Busch and his coworkers , who were interested in the cation binding properties of such ligands. A sequential synthesis was utilized to produce 1,4,8,11-tetrathiacyclotetradecane [tetrathia-14-crown-4 (70)] . In the first step, 1,3-propanedithiol is metallated using sodium and alkylated with 2-chloroethanol. The diol was then treated with thiourea to form the dimercapto-dithioether compound 9. The latter was once again metallated with sodium and allowed to react with 1,3-dibromopropane. The yield of 70 in the ring closure step, conducted at high dilution in absolute ethanol, was 7.5% after recrystallization. The entire sequence is illustrated in Eq. (6.8) . ... 

In a similar way the yields of the 12- to 14-membered tetrathia crown compounds 69a-c were significantly increased by Kellogg and Buter [17], when the dithiols 68 were reacted with 1,2-dibromoethane and 1,3-dibromopropane under dilution conditions [1] by the addition of equimolar amounts of CS2CO3 (Table 8). 

The C ium Effect Syntheses of Medio- and Macrocyclic Compounds Table 8. Yields of the tetrathia crowns 69a-c... 

Indium(III) chloride complexes with tetrathia-crowns, [InCl2(thia-macrocycle)][InCl4] (thia-macrocycle =... 

In particular, the macrocyclic tetrathia-crown ethers L1364-L1366 have been built according to Equation (6.28) [94]. Yields of these substances obtained in the presence of CS2CO3 in DMF amount to 88, 72 and 76%, respectively, and exceed those achieved by the alternative synthetic route in the presence of Na" " by 5-10... 

Abstract Starting with tetracyanodibenzo(l,4,7,10-tetrathia-(12-crown-4)) (1) and 4-nitro-l,2-dicyanobenzene (2), nitro-substituted dimeric phthalocyanine (3) was synthesized. In the second step, using hydrazine hydrate as a reductant, amine-substituted dimeric phthalocyanine (4) was synthesized from nitro-substituted dimeric phthalocyanine. Stractmres of all synthesized compounds were determined by elemental analyses, UV/vis, H-NMR and IR spectroscopy. 

Wolf, R. E., Hartman, J. A. R., Storey, J. M. E., Foxman, B. M., Cooper, S. R., Crown thioether chemistry - structural and conformational studies of Tetrathia-12-Crown-4, Pentathia-15-Crown-5, and Hexathia-18-Crown-6 -implications for ligand design. J. Am. Chem. Soc. 1987, 109, 4328-4335. 

Crown-tetrathia[3.3.3.3]metacyclophanes 118-120, which have two crown moieties and one metacyclophane unit, have been prepared via intermolecular coupling reactions <2005T9248> as shown in Scheme 18. The X-ray crystal analysis of 119 showed that the compound adopted a perpendicular conformation in which two aromatic rings were inclined to be perpendicular to the opposite aromatic rings. The variable-temperature ll NMR spectra for 119 and 118 suggested that the energy barrier for interconversion of 119 was estimated to be 12.1 kcalmol-1, whereas 118 showed two non-interconvertible conformers at room temperature, which tended to interconvert at elevated temperature however, many conformers coexisted at low temperature. 

Shamsipur M, Mashhadizadeh MH, Azimi G. Highly selective and efficient transport of mercury(II) ions across a bulk liquid membrane containing tetrathia-12-crown-4 as a specific ion carrier. Sep Purif Technol 2002 11. 155-161. 

Mashahadizadeh MH, Mohyaddini R, Shamsipur M. Selective and efficient hquid membrane transport of Au(in) by tetrathia-12-crown-4 as a specific carrier. Sep Purif Technol 39 2004 161-166. 

Hexaazadecalin photoelectron spectra, 3, 543 2,4,12,20,22,30-Hexaaza-1,5,13,29-tetrathia[l,2-30]-[5.2.3.2]paracyclophane nomenclature, 1, 27 Hexabenzof 18]crown-6 complexes, 7, 742 c/s, trans-2,4-Hexadiene synthesis, 1, 431 trans, trarts-2,4-Hexadiene synthesis, 1, 431 Hexahelicene... 

Moyer et al. [8] performed a systematic study of the impregnation of a macrocycle, tetrathia-l4-crown-4 (TT14CA), onto polystyrene-divinylbe-nzene sulfonic acid (PS-DVB) strong-acid resin beads to obtain an SIR for extraction of Cu(II) from sulfuric acid. Four different impregnation procedures were tested, as can be seen in Fig. 4. In their study the effects of different parameters, such as the organic solvent used and hydration steps, were tested in order to improve the copper extraction ability. 

Moyer et al. [8] presented a novel synergistic study of the extraction of Cu(II) from sulfuric acid by using an impregnated resin prepared by adsorption of a tetradentate macrocyclic ionophore, tetrathia-l4-crown-4... 

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