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With potassium carbonate In dichloromethane; water for 5h; |
Amiodarone derived thianthrenium salt 10a
Under an ambient atmosphere, a 20 ml glass-vial was charged with amiodarone hydrochloride 10-HCI (500 mg, 0.73 mmol, 1.47 equiv.), DCM (5.0 ml, c = 0.15 M), and aqueous K2C03solution (ca. 10 ml, 10 % w/w). After stirring for 5 h, the layers were separated. The organic layer was evaporated to dryness, and the residue was dried in vacuo to afford amiodarone 10 as a free base. Under an ambient atmosphere, a 20 ml glass-vial was charged with amiodarone 10 (340 mg, 0.500 mmol, 1 .00 equiv.), and dry MeCN (2.0 ml, c = 0.25 M). HBF4OEt2(102 pi, 0.12 g, 0.75 mmol, 1 .5 equiv.), and triflu oroacetic anhydride (0.21 ml, 0.32 g, 1 .5 mmol, 3.0 equiv.) were added sequentially while stirring the reaction mixture. After cooling to 0 °C, tetrafluorothianthrene reagent (97 % (w/w) tetrafluorothianthrene-S-oxide 1 , 3 % (w/w) tetrafluorothianthrene 2, 157 mg, 0.50 mmol, 1 .0 equiv.) was added in one portion, followed by the addition of HBF4-OEt2(82 mI, 97 mg, 0.60 mmol, 1.2 equiv.) in one portion at 0 °C, leading to a purple suspension. The vial was sealed with a screw-cap, and the mixture was stirred at 0 °C for 1 h, followed by stirring at 25 °C for 2 h, until a slight purple solution was obtained. The reaction mixture was concentrated under reduced pressure, and diluted with 5 ml DCM. The DCM phase was poured onto an aqueous K2C03solution (ca. 10 ml, 10 % w/w). The mixture was poured into a separatory funnel, and the layers were separated. The DCM layer was washed with aqueous NaBF4solution (2 x ca. 10 ml, 5 % w/w), and with water (2 x ca. 10 ml). The DCM layer was dried over Na2S04, filtered, and the solvent was removed under reduced pressure. The residue was purified by chromatography on silica gel eluting with DCM / /-PrOH (30:1 (v/v)). The product was dissolved in 5 ml DCM, and precipitated with 20 ml Et20. The suspension was decanted, and the solid was dried in vacuo to afford 469 mg (92 %) of 10a as colorless foam.NMR Spectroscopy:1H NMR (500 MHz, CD3CN, 298 K, d): 8.48 (dd, J = 9.1 Hz, 7.1 Hz, 2H), 8.15 (s, 2H), 7.97(dd, J = 9.8 Hz, 7.0 Hz, 2H), 7.63 (d, J = 8.7 Hz, 1 H), 7.48 (d, J = 2.0 Hz, 1 H), 7.15 (dd, J = 8.6 Hz, 2.0 Hz, 1 H), 4.35 (t, J = 5.0 Hz, 2H), 3.70 (t, J = 5.1 Hz, 2H), 3.44 (q, J = 7.3 Hz, 4H), 2.72 (t, J = 7.8 Hz, 2H), 1 .69 - 1 .62 (m, 2H), 1.37 (t, J = 7.3 Hz, 6H), 1.26 (ijjsext, J = 7.4 Hz, 2H), 0.83 (t, J = 7.4 Hz, 3H).13C {1H} NMR (126 MHz, CD3CN, 298 K, d): 187.8, 170.7, 161 .3, 154.8 (dd, J = 262.1 , 13.1 Hz), 154.0, 151 .6 (dd, 255.7 Hz, 13.6 Hz), 141 .4, 135.2 (dd, J = 8.6 Hz, 3.8 Hz), 132.7, 125.7 (dd, J = 22.3 Hz, 1 .5 Hz), 124.7, 124.0, 121.2 (dd, J = 21 .8 Hz), 1 19.0, 1 16.9, 1 15.7 (dd, J = 7.2 Hz, 3.3 Hz), 1 13.1 , 91.5, 67.8, 52.6, 49.6, 30.3, 29.0, 23.1 , 13.9, 9.5.19F {1H} NMR (471 MHz, CD3CN, 298 K, d): -126.1 (d, J = 20.6 Hz), -134.4 (d, J = 20.2 Hz), -151 .6 (bs), -151.7 (bs).HRMS-ESI(m/z) calc’d for C37H32F4l2N03S2+[M-BF4]+, 931.985300; found, 931 .984373; deviation: 1 .0 ppm. |
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