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Tri4-[ethyl 4-(4-di(phenylene ethynylene)-phenoxy)butyrate] phosphane sulfide 4: A solution of 2 (50 mg, 0.14 mmol) and 3 (385 mg, 0.88 mmol) in toluene, 5 mL) and NEt3 (1.5 mL) was degassed with argon. Pd(PPh3)4 (8 mg, 0.007 mmol) and CuI (2 mg, 0.007 mmol) were added quickly under argon and the resulted mixture is stirred under argon at 50°C for 20h. The reaction was then quenched with a solution of aqueous NH4Cl sat, 5 mL, After extraction (AcOEt, the organic layer was dried (Na2SO4, filtrated and evaporated under vacuum. The crude mixture was then purified by flash chromatography (eluant: cyclohexane, dichloromethane: 2: 1 to AcOEt 100, to afford a brown solid (115 mg, 64, Rf: 0,2 (cyclohexane, dichloromethane: 8:2, 1H NMR: CDCl3 δ (ppm) 7.74-7.67 (m, 6H, 7.62-7.58 (m, 6H, 7.53-7.43 (m, 18H, 6.88-6.85 (dd, J, 6.9Hz and 2Hz, 6H, 4.15 q, J, 7.2 Hz
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+ 1285.4472, found: 1285.4525.
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16944365890
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35648971054
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To a solution of ethyl 4-(4-ethynyl-phenoxy)-butyrate (780 mg, 3.36 mmol) in anhydrous toluene 40 mL and NEt3 (12 mL) under argon, 1,4-diiodobenzene (3.3g, 10 mmol) was added and the solution was then degassed with argon. Pd(PPh3)4 (194 mg, 0.168 mmol) and Cul (32 mg, 0.168 mg) were added quickly and the reaction mixture was stirred at 50°C for 20h. Then the reaction was quenched with 20 mL of AcOEt and 25 mL of an aqueous NH4Cl sat. solution. After extraction, drying (Na2SO4, filtration and evaporation the resulting crude mixture was purified by flash chromatography (eluant: cyclohexane 100% to Cyclohexane, CH2Cl2: 1/1) to afford the desired product 3 as a white solid (757 mg, 51, mp: 100, Rf: 0.25 (cyclohexane/dichloromethane; 1: 1, 1H NMR: CDCl3 δ (ppm) 7.68 (2H, d, J, 8.7 Hz, 7.44 (2H, d, J, 7.9 Hz, 7.23 (2H, d, J, 8.5 Hz, 6.85 2H, d, J, 8.0 Hz, 4.1
-
3 δ (ppm) 173.1, 159.1, 137.4, 133.1, 123.1, 115.0, 114.5, 93.6, 90.8, 87.2, 66.8, 60.5, 30.7, 24.5, 14.2. Elemental Analysis: calc. %C = 55.31%; %H = 4.41% - found %C = 55.74%; %H = 4.70%.
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