1,4-dibromo-2,5-diiodobenzene

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 1 L three-necked flask fitted with a mechanical stirrer were added 16.7 g (73.0 mmol) of periodic acid and 525 ml of sulfuric acid. After periodic acid was dissolved, 36.4 g (219 mmol) of potassium iodide was added portionwise. The content was cooled to a temperature of −30° C. and 34.5 g (146 mmol) of 1,4-dibromobenzene was added over a period of 5 minutes. The resulting mixture was stirred at −30 to −20° C. for 36 hours. After the reaction mixture was poured into ice (2 kg), the whole was filtrated and a solid was taken out. The solid was dissolved in chloroform, the solution was washed with a 5% aqueous sodium hydroxide solution and water, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to obtain white crystals of 1,4-dibromo-2,5-diiodobenzene (36.0 g, yield 50%). To a 1 L three-necked flask fitted with a mechanical stirrer was added over a period of 5 minutes the whole was filtrated The solid was dissolved in chloroform the solution was washed with a 5% aqueous sodium hydroxide solution and water the organic phase was dried over anhydrous magnesium sulfate After concentration under reduced pressure the residue was recrystallized from chloroform

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A oven dried 2000 cm3 flask is charged with 1,4-dibromo-2,5-diiodobenzene (61.00 g, 125.1 mmol), dichlorobis(triphenylphosphine)palladium(II) (2.195 g, 3.127 mmol) and anhydrous tetrahydrofuran (300 cm3). Once the starting materials are dissolved, a solution of 0.5 M of 3-bromo-2-thienylzinc bromide in tetrahydrofuran (500 cm3, 250.2 mmol) is transfered using a canula and the reaction heated to 85° C. for 3 hours. The reaction is cooled down overnight and the white precipitate filtered off. This precipitate is washed with water (750 cm3) and methanol (250 cm3) to obtain 25.77 g of the title product. Further product is recovered from the initial filtrate. The filtrate is reduced to ca. 90 cm3 in vacuo and then 500 cm3 of methanol is added. The precipitate is filtered off, washed with water (750 cm3) and methanol (250 cm3) and finally triturated three times in hot propan-2-ol to obtain an additional 12.72 g of the title product. (38.49 g, Yield: 55%). NMR (1H, 300 MHz, CDCl3): δ 7.71 (s, 2H); 7.42 (d, J=5.3 Hz, 2H); 7.09 (d, J=5.3 Hz, 2H). NMR (13C, 75 MHz, CDCl3): δ 136.62; 136.10; 135.16; 130.50; 126.97; 123.52; 111.78. A oven dried 2000 cm3 flask Once the starting materials are dissolved The reaction is cooled down overnight the white precipitate filtered off This precipitate is washed with water (750 cm3) and methanol (250 cm3)

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A oven dried 2000 cm3 flask is charged with 1,4-dibromo-2,5-diiodobenzene (61.00 g, 125.1 mmol), dichlorobis(triphenylphosphine)palladium(II) (2.195 g, 3.127 mmol) and anhydrous tetrahydrofuran (300 cm3). Once the starting materials are dissolved, a solution of 0.5 M of 3-bromo-2-thienylzinc bromide in tetrahydrofuran (500 cm3, 250.2 mmol) is transfered using a canula and the reaction heated to 85° C. for 3 hours. The reaction is cooled down overnight and the white precipitate filtered off. This precipitate is washed with water (750 cm3) and methanol (250 cm3) to obtain 25.77 g of the title product. Further product is recovered from the initial filtrate. The filtrate is reduced to ca. 90 cm3 in vacuo and then 500 cm3 of methanol is added. The precipitate is filtered off, washed with water (750 cm3) and methanol (250 cm3) and finally triturated three times in hot propan-2-ol to obtain an additional 12.72 g of the title product. (38.49 g, Yield: 55%). NMR (1H, 300 MHz, CDCl3): δ 7.71 (s, 2H); 7.42 (d, J=5.3 Hz, 2H); 7.09 (d, J=5.3 Hz, 2H). NMR (13C, 75 MHz, CDCl3): δ 136.62; 136.10; 135.16; 130.50; 126.97; 123.52; 111.78. A oven dried 2000 cm3 flask Once the starting materials are dissolved The reaction is cooled down overnight the white precipitate filtered off This precipitate is washed with water (750 cm3) and methanol (250 cm3)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under nitrogen atmosphere, 1,4-dibromo-2,5-diiodobenzene (3.0 g, 6.2 mmol) was dissolved in diisopropylamine (45 ml) and anhydrous benzene (45 ml), followed by stirring for 30 minutes. Copper iodide (235 mg, 0.12 mmol), PdCl2(PPh3)2 (430 mg, 0.61 mmol), and 1-dodecene (1.9 ml, 12.9 mmol) were added to the mixture, followed by stirring at room temperature for 14 hours. The reaction liquid was poured into water and extracted with chloroform, and the obtained organic layer was washed with 200 ml of water three times. The resulting organic layer was dried over anhydrous sodium sulfate and purified by a column chromatography (silica gel and methylene chloride:hexane=1:3), followed by recrystallization in ethanol, thereby colorless powdery 1,4-dibromo-2,5-bis(octyne-1-yl)benzene was obtained (1.56 g, yield: 56%). by stirring at room temperature for 14 hours The reaction liquid extracted with chloroform the obtained organic layer was washed with 200 ml of water three times The resulting organic layer was dried over anhydrous sodium sulfate purified by a column chromatography (silica gel and methylene chloride:hexane=1:3) followed by recrystallization in ethanol

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 1 L three-necked flask fitted with a mechanical stirrer were added 16.7 g (73.0 mmol) of periodic acid and 525 ml of sulfuric acid. After periodic acid was dissolved, 36.4 g (219 mmol) of potassium iodide was added portionwise. The content was cooled to a temperature of −30° C. and 34.5 g (146 mmol) of 1,4-dibromobenzene was added over a period of 5 minutes. The resulting mixture was stirred at −30 to −20° C. for 36 hours. After the reaction mixture was poured into ice (2 kg), the whole was filtrated and a solid was taken out. The solid was dissolved in chloroform, the solution was washed with a 5% aqueous sodium hydroxide solution and water, and the organic phase was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was recrystallized from chloroform to obtain white crystals of 1,4-dibromo-2,5-diiodobenzene (36.0 g, yield 50%). To a 1 L three-necked flask fitted with a mechanical stirrer was added over a period of 5 minutes the whole was filtrated The solid was dissolved in chloroform the solution was washed with a 5% aqueous sodium hydroxide solution and water the organic phase was dried over anhydrous magnesium sulfate After concentration under reduced pressure the residue was recrystallized from chloroform