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Synthesis ofFluorinated Calix[4]arene Reagents The chemical structures of three sulfur-containing fluorinated calixarenes are given in Figure 2, alongside the tetra-hydroxamate (C 1). The synthesis of upper rim allyl calixarenes, for subsequent thiolene addition reaction to yield fluorinated derivatives, has been reported elsewhere by members of this laboratory (22). Synthetic methods for lower rim functionalization, to provide donor atoms for selective metal ion complexation, such as for Fe(III) with hydroxamate (C1) and for Ag(I) with thioamide groups (C2), are now also well established. As the emphasis in this work is on the application of these macrocyclic reagents for gold extraction, only the synthesis of the novel lower rim fluorinated derivative and the most effective reagent (C4) is given below. Synthesis ofp-t-butylcalix[4]arenetetra-l- heptadecafluorodecylthio-n-propyl-3-(2-ethyJ)- 2-thiourea acetate (C4) To 0.8 g (0.005 moles) HOCH2CH2NH (C=S)NHCH2CH=CH2 (Aldrich) was added 2.4 g (0.005 moles) heptadecafluorodecanethiol (22) in 6.0 g 1,2-dichloroethane and 200 mg AIBN. The entire mixture was refluxed under nitrogen for 2 h following which a further 200 mg of azoisobutyronitrile was added and a further 2 h period of reflux was carried out. After cooling, all volatiles were removed to give a buff- coloured waxy solid of HOCH2CH2NH (C=S)NH(CH2hS(CH2)2(CF2hCF3 (3.15 g, 98% yield). IH -NMR spectral analysis verified the absence of a chemical shift resonance at 5.92m for =CH from the allyl functionality of the reactant. The above compound (1.58 g) was purified further by sequential chromatography on neutral alumina eluting first with methylene chloride to remove solvent front and high Rf impurities and, subsequently, with methylene chloride/methanol (14:1) to give a pale yellow solid with R, 0.22 (0.6 g, 38% yield). CHN Analysis: Found (%): C, 41.90; H, 4.01; N, 3.37; S, 7.53. C116HI24NsSSOI2F6S' Theory (%): C, 41.33; H, 3.71; N, 3.33; S, 7.61. Instrumentation Used for Supercritical Fluid Extraction Extractions were performed using an Isco SFX® supercritical fluid extraction system (Isco Inc., USA, supplied by Jones Chromatography, UK). The SFE system was controlled by the 260D Series Pump controller and consisted of a syringe pump and heated extractor block. A heated variable restrictor was used and the flow rate was set at 1.0 ml min-I. Extracted samples were collected in a liquid-trap containing MIBK or DMSO. The various working pressures were recorded in atmospheres and the temperature of the extractor was set manually. Analysis and detection of extracted samples were carried out using a Pye Unicam SP9 atomic absorption spectrometer and unmodified SF-C02 was used for all extractions. Solubility Measurements o fLigands in Supercritical CO Solubility measurements of each reagent were carried out using the Isco SFE system. A weighed amount (ca 80 mg) was placed in an open-ended glass tube (3 x 0.5 em Ld.). The sample tube was plugged with glass wool at both ends and inserted into the extraction cell (2.5 ml) reducing the volume of the cell to 2.2 ml. The sample was statically extracted at 60°C under 200 or 300 atm of SF-C02 for 30 min. After this time, the fluid was vented into a collection vial containing 5 ml of MIBK or DMSO. The sample tube was removed To 0.55 g (0.000625 mole) p-tert-butylcalix [4]arene tetraacetic acid was added 5 ml thionyl chloride and the entire mixture was refluxed, with stirring, for 2 h (calcium chloride tube attached during reaction period). After this period, all the volatiles were removed under reduced pressure to give the from the cell and weighed. The solubility was corresponding p- tert-butylcalix [4]arene tetra-acid chloride. To this solid was added 10 ml dry THF, followed by 0.198 g (0.0025 mole) dry pyridine and 1.6 g (0.0025 mole) HOCH2CH2NH (C=S)NH(CH2hS(CH2)2(CF2hCF3 in 5 ml dry THF and the entire mixture was stirred at room temperature overnight under nitrogen. Following this time, all volatiles were removed and the residual pale yellow solid was washed with 5% aqueous HCl and then water. The resulting sample was allowed to air dry overnight to afford 2.0 g of the crude product as a pale yellow solid. calculated from the loss in weight of the sample tube divided by the volume of the extraction cell and given in terms of mmol of sample per litre of CO2. (fji;} ColdBulletin 1999,32(2) 55 2 SFE ofAu(III) Irom Solid Supports Cellulose filter paper is a convenient material for studies of the metal extractive ability of designed reagents using supercritical fluid extraction. For the SFE of gold, 40/-11 of gold (1000 ppm gold (III) chloride standard) was spiked onto the filter paper (3x1em). The filter paper was allowed to dry in air for 30 min and was then loaded into the glass tube alongPDF Image | Carrying Gold in Supercritical C02
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