77% |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 80℃; for 12h;Inert atmosphere; |
Under nitrogen protection, add to a 300ml two-neck flask2,7-dibromo-9,9-dioctylfluorene(5.48g, 10mmol),4-(4,4,5,5-tetramethyl-1,3-dioxa-2-boryl)triphenylamine(2.89 g, 10 mmol), potassium carbonate (3.45 g,25mmol), tetrakis(triphenylphosphine)palladium (0.58g, 0.5mmol), 12ml deionized water and 120ml toluene, heating to 80C12 hours.After the reaction was completed, the product was extracted with methylene chloride and washed three times with a saturated aqueous solution of sodium chloride. After removing the solvent of the organic phase, the crude product was eluted with a mixture of petroleum ether:dichloromethane = 8:1 (v/v). Purification by column chromatography gave 5.51 g of a nearly white solid with a yield of 77%. |
74.2% |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 90℃;Inert atmosphere; |
As shown in Scheme 1, the triphenylamine 4-borate (0.371 g, 1 mmol) and 9,9-dioctyl-2,7-dibromofluorene (1.192 g, 2 mmol) were dissolved in 15 mL of toluene, into which K2CO3 water solution (2 M, 10 mL) was dropped. Then, tetrakistriphenylphosphine palladium (Pd(PPh3)4) (0.057 g, 0.05 mmol) was added to the above reaction mixture. After refluxing for 4 h under nitrogen protection, the reaction mixture was poured into water and extracted with dichloromethane. The collected organic layer was dried over anhydrous MgSO4 and concentrated under reduced pressure. Finally, the resultant residue was purified by silica gel column chromatography using mixture eluents of ethyl acetate and hexane (1:20, v/v), which afforded M1 as intermediate product (0.3123 g, 74.2%, C47H54BrN: C 79.22, H 7.59, Br 11.22, N 1.97; found: C 79.17, H7.72, Br 11.22, N 1.97). 1H NMR (600 MHz, DMSO) δ 7.86 (d, J = 7.9 Hz, 1H), 7.77 (d, J = 8.1 Hz, 1H), 7.72 (d, J = 1.3 Hz, 1H), 7.64 (ddd, J = 16.5, 10.7, 8.7 Hz, 4H), 7.51 (dd, J = 8.0, 1.8 Hz, 1H), 7.36-7.29 (m, 4H), 7.10-7.02 (m, 8H), 2.04 (tt, J = 13.3, 8.3 Hz, 4H), 1.25-0.95 (m, 20H), 0.75 (t, J = 7.2 Hz, 6H), 0.49 (s, 4H). 13C NMR (101 MHz, CDCl3) δ 153.15, 151.59, 150.98, 147.68, 147.63, 147.17, 147.00, 139.93, 139.87, 139.73, 139.32, 138.86, 135.63, 135.31, 129.94, 129.27, 128.99, 127.76, 127.27, 126.10, 125.63, 125.50, 124.37, 124.32, 124.28, 124.13, 124.04, 123.93, 122.94, 122.87, 122.79, 122.64, 120.97, 120.86, 120.02, 119.89, 58.36, 55.44, 55.19, 40.47, 40.30, 31.75, 30.02, 29.93, 29.18, 29.15, 23.69, 22.58, 18.38, 14.06. |