4-BROMO-2,1,3-BENZOTHIADIAZOLE

To a flask equipped with a reflux device, 25.0 g (183.7 mmol) of the compound (a), and 150 mL of 48percent hydrobromic acid were added. After heating to 100° C., 8.5 mL (165.4 mmol) of bromine was dropped, the resultant was stirred at 100° C. for nine hours, and then it was let cool. After a reaction was finished, 200 mL of dichloromethane was added, precipitated solid was dissolved, and further 100 mL of an aqueous sodium sulfate solution was added. An organic layer was collected, washed with a saturated aqueous sodium hydrogen carbonate solution, dried with anhydrous sodium sulfate, and then a solvent was removed under reduced pressure to obtain an unrefined compound (b). The compound (b) was suspended in 200 mL of hexane/ethyl acetate (4:1, volume ratio), remaining solids were filtered to thereby remove 4, 7-dibromo-2, 1, 3-benzothiadiazole being a by-product. The filtrate was condensed again, suspended in 200 mL of hexane, and remaining solids were filtered, to thereby obtain 11.2 g of the compound (b). Further, the filtrate was condensed, and refinement was performed by a column chromatography method using hexane/ethyl acetate (97:3, volume ratio) as a developing solution, to thereby obtain 8.0 g of the compound (b). A sum total was 19.2 g (89.3 mmol), and a yield was 49percent.To a flask equipped with a reflux device, 25.0 g (183.7 mmol) of the compound (a), and 150 mL of 48percent hydrobromic acid were added. After heating to 100° C., 8.5 mL (165.4 mmol) of bromine was dropped, the resultant was stirred at 100° C. for nine hours, and then it was let cool. After a reaction was finished, 200 mL of dichloromethane was added, precipitated solid was dissolved, and further 100 mL of an aqueous sodium sulfate solution was added. An organic layer was collected, washed with a saturated aqueous sodium hydrogen carbonate solution, dried with anhydrous sodium sulfate, and then a solvent was removed under reduced pressure to obtain an unrefined compound (b). The compound (b) was suspended in 200 mL of hexane/ethyl acetate (4:1, volume ratio), remaining solids were filtered to thereby remove 4, 7-dibromo-2, 1, 3-benzothiadiazole being a by-product. The filtrate was condensed again, suspended in 200 mL of hexane, and remaining solids were filtered, to thereby obtain 11.2 g of the compound (b). Further, the filtrate was condensed, and refinement was performed by a column chromatography method using hexane/ethyl acetate (97:3, volume ratio) as a developing solution, to thereby obtain 8.0 g of the compound (b). A sum total was 19.2 g (89.3 mmol), and a yield was 49percent.In a first step, 10 g (73.52 mmol) of 2, 1, 3-benzothiadiazole (1) was added to a 100 ml round-Suspended in 50 ml HBr solution (48percent), A solution of 2.8 ml (54.26 mmol) of bromine was added dropwise with vigorous stirring, After all the drops were added, the mixture was heated to 150 ° C and refluxed for 2 hours.After completion of the reaction, the mixture was cooled to room temperature, The reaction mixture was poured into 500 ml of water, The precipitated solid was filtered to give 10.4 g of crude product;The crude product contains a small amount of dibromo substituted product as well as the starting material.The crude product is directly put into the next step.Under nitrogen protection, To a 500 ml two-necked round bottom flask equipped with a condenser tube was added 8.556 g of crude product (assuming all 4-bromo-2, 1, 3-benzothiadiazole (2), 40 mmol)10.208 g (44 mmol) of 4-formylphenylboronic acid pinacol ester, 2.32 g (2.0 mmol) of tetrakis (triphenylphosphine) palladium and 200 ml of THF, Followed by the addition of 200 ml of an aqueous solution of potassium carbonate (11.06 g, 80 mmol), heated to reflux and stirred for 12 h.After completion of the reaction, the mixture was cooled to room temperature and the mixture was extracted three times with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent under reduced pressure was treated with dichloromethane / petroleum ether (2: 1) as the eluent, Silica gel column chromatography afforded 8.2 g of pale yellow 4-formylphenyl-2, 1, 3-benzothiadiazole (3).Under nitrogen protection, 1000m with mechanical stirring, thermometer and condenserAdd product to L four-neck bottle9, 10-bis(2-naphthyl)indole-2-pinacol borate (compound B1) 50 g (0.09 mol, 1 eq), A mixture of [9, 9-bis(2-{2-methoxyethoxy}ethyl)-9H-fluoren-2-yl]boronic acid [J. Mater. Chem. C, 2015, 3, 9412 - 9424] (92 mg, 0.222 mmol), 4-bromobenzo[c] [l, 2, 5]thiadiazole [J. Phys. Chem. B, 2012, 116, 7259-7268] (38 mg, 0.177 mmol), and potassium carbonate (194 mg, 3.46 mmol) in toluene (10 mL), ethanol (1 mL), and water (2 mL) was placed under vacuum until boiling and backfilled with argon three times. Tetrakis(triphenylphosphine)palladium(0) (10 mg, 0.009 mmol) was added and the solution heated in an oil bath held at 110 °C overnight under a blanket of argon. The solution when then cooled, diluted with water (20 mL), ethyl acetate (20 mL), and the layers separated. The aqueous solution was extracted with ethyl acetate (3 x 20 mL), and the combined organic extracts washed with brine (20 mL), dried over anhydrous sodium sulphate, filtered, and the solvent removed in vacuo. The crude residue was purified by column chromatography over silica using an ethyl acetate:light petroleum mixture (1 :3) as eluent followed by a dichloromethane: diethyl ether mixture (1 : 1) to afford AL03-79 as a yellow/green oil after removal of the solvent (48 mg, 52percent). 1H NMR (500 MHz, CDC13) delta: 2.42-2.55 (4H, m, GIH), 2.80-2.93 (4H, m, GIH), 3.20-3.23 (4H, m, GIH), 3.25 (6H, s, GIH), 3.27-3.32 (4H, m, GIH), 7.32-7.40 (2H, m, FIH), 7.45-7.48 (1H, m, FIH), 7.72 (1H, dd, / = 7.0, 8.5 Hz, BTH), 7.74-7.76 (1H, m, FIH), 7.78 (1H, dd, 7 = 1.0, 7.0 Hz, BTH), 7.84 (1H, dd, = 0.5, 8.0 Hz, BTH), 7.97-7.99 (1H, m, FIH), 8.00 (1H, d, = 1.0 Hz, FIH), 8.02-8.03 (1H, m, FIH). HRMS (ESI-MS) for C29H32N2O4S [M + Na]+ Calcd: 527.1975 (100percent), 528.2009 (31percent). Found: 527.1997 (100percent), 528.2021 (34percent).A mixture of (9, 9-di-n-hexyl-9H-fluoren-2-yl)boronic acid [J. Am. Chem. Soc, 2004, 126, 13695-13702] (915 mg, 2.42 mmol), 4-bromobenzo[c] [l, 2, 5]thiadiazole [J. Phys. Chem. B, 2012, 116, 7259-7268] (434 mg, 2.02 mmol), and potassium carbonate (1.20 g, 8.70 mmol) in toluene (20 mL), ethanol (8 mL), and water (12 mL) was placed under vacuum until boiling and backfilled with argon six times. Tetrakis(triphenylphosphine)- palladium(O) (100 mg, 0.087 mmol) was added and the solution heated in an oil bath held at 100°C overnight under a blanket of argon. The solution when then cooled, diluted with water (90 mL), diethyl ether (90 mL), brine (60 mL), and the layers separated. The aqueous solution was extracted with diethyl ether (3 x 60 mL) and the combined organic extracts were washed with water (2 x 60 mL), brine (60 mL), dried over anhydrous magnesium sulphate, filtered on a silica plug, and the solvent removed in vacuo. The crude residue was purified by column chromatography over silica using a dichloromethane: light petroleum mixture (0: 1 to 1 : 10) as eluent to afford AL03-77 as yellow/green oil after removal of the solvent (751 mg, 79percent). 1H NMR (500 MHz, CDC13) delta: 0.66-0.83 (10H, m, HexH), 1.00- 1.12 (12H, m, HexH), 1.95-2.09 (4H, m, HexH), 7.31- 7.40 (3H, m, FIH), 7.71 (1H, dd, = 8.5, 8.5 Hz, BTH), 7.76 (2H, dd, = 1.0, 7.0 Hz, FIH), 7.85 (1H, dd, = 0.5, 8.0 Hz, BTH), .90 (1H, d, = 0.5 Hz, BTH), 7.97 (1H, dd, = 1.5, 8.0 Hz, FIH), 8.00 (1H, dd, = 1.0, 8.5 Hz, FIH). HRMS (ESI-MS) for C31H36N2S [M + Na]+ Calcd: 491.2491 (100percent), 492.2522 (34percent), 493.2511 (10percent). Found: 491.2491 (100percent), 492.2500 (40percent), 493.2480 (12percent).

Molecular Weight:215.07
XLogP3:2.5
Hydrogen Bond Acceptor Count:3
Exact Mass:213.92003
Monoisotopic Mass:213.92003
Topological Polar Surface Area:54
Heavy Atom Count:10
Complexity:133
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes