1-bromo-4-hexylbenzene

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis-(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100° C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography. the mixture is extracted twice with methyl t-butyl ether (100 ml) The combined organic phases are washed with water dried over sodium sulfate evaporated in vacuo The residue is purified by column chromatography

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-hexylbenzene (500 mg, 1.7 mmol) in THF (15 mL) at −78° C. was added t-butyllithium (1.7 M in pentane, 2.0 mL) slowly dropwise. After stirring at −78° C. for 1 h, trimethyl borate (0.39 mL, 3.46 mmol) was added. The reaction mixture was warmed at RT over 2 h. After stirring at RT for 15 min, the reaction mixture was quenched with saturated solution of ammonium chloride and extracted with ethyl acetate. The combined organic layers were washed with HCl (10% solution), brine, and dried (MgSO4), filtered, and concentrated under reduce pressure to give 415 mg (4-hexylphenyl)boronic acid as a colorless solid. A solution of the resulting boronic acid (962 mg, 4.07 mmol) and Intermediate 3 (1.1 g, 4.27 mmol) in toluene (37 mL), methanol (1.2 mL) and water (2 mL) were added potassium carbonate (1.09 g, 8.45 mmol) and LiCl (181 mg, 4.27 mmol) with stirring. After bubbling with Ar for 10 min, tetrakis(triphenylphosphine)palladium(0) (99 mg) was added and heated at 95° C. for 16 h. After the reaction mixture was cooled at RT, it was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, and dried (MgSO4), filtered, and concentrated under reduce pressure. The residue was purified by MPLC (15% ethyl acetate in hexanes) gave 1.16 g of Intermediate 6 as colorless solid. The reaction mixture was warmed at RT over 2 h After stirring at RT for 15 min the reaction mixture was quenched with saturated solution of ammonium chloride extracted with ethyl acetate The combined organic layers were washed with HCl (10% solution), brine dried (MgSO4) filtered concentrated

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100° C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography. the mixture is extracted twice with methyl t-butyl ether (100 ml) The combined organic phases are washed with water dried over sodium sulfate evaporated in vacuo The residue is purified by column chromatography

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100° C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography. the mixture is extracted twice with methyl t-butyl ether (100 ml) The combined organic phases are washed with water dried over sodium sulfate evaporated in vacuo The residue is purified by column chromatography

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

Procedure: is prepared analogously to Reference 14 (p. 16) from 6-methoxybenzo[b]thiophene-2-boronic acid and 4-hexylbromobenzene in a Suzuki reaction. The 2-(4-hexylphenyl)-6-methoxybenzo[b]thiophene obtained as the primary product is subjected to ether cleavage by means of hydrobromic acid/glacial acetic acid. The resultant hydroxyl compound gives the target compound in a Williamson ether synthesis using octyl bromide in 2-butanone in the presence of potassium carbonate.

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-hexylbenzene (500 mg, 1.7 mmol) in THF (15 mL) at −78° C. was added t-butyllithium (1.7 M in pentane, 2.0 mL) slowly dropwise. After stirring at −78° C. for 1 h, trimethyl borate (0.39 mL, 3.46 mmol) was added. The reaction mixture was warmed at RT over 2 h. After stirring at RT for 15 min, the reaction mixture was quenched with saturated solution of ammonium chloride and extracted with ethyl acetate. The combined organic layers were washed with HCl (10% solution), brine, and dried (MgSO4), filtered, and concentrated under reduce pressure to give 415 mg (4-hexylphenyl)boronic acid as a colorless solid. The reaction mixture was warmed at RT over 2 h After stirring at RT for 15 min the reaction mixture was quenched with saturated solution of ammonium chloride extracted with ethyl acetate The combined organic layers were washed with HCl (10% solution), brine dried (MgSO4) filtered concentrated

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

Procedure: A 3 L-volume four-necked flask equipped with a Dimroth condenser, a dropping funnel and a stirrer was charged with magnesium (15.7 g, 0.645 moles, in a flaky state), and the inside of the flask was purged with nitrogen. Diethyl ether (200 mL) was poured while keeping the inside of the flask at a positive pressure, and one piece of iodine was added while stirring. Furthermore, 1-bromo-4-hexylbenzene (160.9 g, 0.665 moles) and diethyl ether (500 mL) were charged into the dropping funnel while keeping the inside of the flask at a positive pressure. When the flask was heated, and refluxing started, the diethyl ether solution of 1-bromo-4-hexylbenzene was dropped from the dropping funnel under mild refluxing over about 4.5 hours, and the mixture was stirred for one hour as it was. After finishing stirring under heating, the reaction solution was cooled to room temperature and diluted with toluene. Tetrachlorosilane (44.6 g, 0.263 moles) and toluene (200 mL) were charged into the dropping funnel while keeping the inside of the flask at a positive pressure and dropped at room temperature over about 30 minutes. After completion of the dropping, stirring of the reaction solution was continued at room temperature overnight. A formed crystal of magnesium bromide was filtered, and the obtained filtrate was concentrated. The concentrated liquid was distilled in vacuo to obtain bis(4-hexylphenyl)dichlorosilane as a major distillate. This compound was confirmed to be the desired silane compound (aromatic monomer (B2) from chemical shift, branching and integration values of signals obtained by the 1HNMR measurement. In the following polymerization reaction, a purified material obtained by vacuum distillation of this major distillate just before that was provided. Also, all of the solvents to be used were dried by a molecular sieve and then used. A 3 L-volume four-necked flask equipped with a Dimroth condenser, a dropping funnel and a stirrer in a flaky state), and the inside of the flask was purged with nitrogen Diethyl ether (200 mL) was poured was added When the flask was heated refluxing under mild refluxing over about 4.5 hours the mixture was stirred for one hour as it After finishing stirring under heating dropped at room temperature over about 30 minutes After completion of the dropping, stirring of the reaction solution A formed crystal of magnesium bromide was filtered the obtained filtrate was concentrated The concentrated liquid was distilled in vacuo

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis-(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100° C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography. the mixture is extracted twice with methyl t-butyl ether (100 ml) The combined organic phases are washed with water dried over sodium sulfate evaporated in vacuo The residue is purified by column chromatography

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 4-bromo-1-hexylbenzene (500 mg, 1.7 mmol) in THF (15 mL) at −78° C. was added t-butyllithium (1.7 M in pentane, 2.0 mL) slowly dropwise. After stirring at −78° C. for 1 h, trimethyl borate (0.39 mL, 3.46 mmol) was added. The reaction mixture was warmed at RT over 2 h. After stirring at RT for 15 min, the reaction mixture was quenched with saturated solution of ammonium chloride and extracted with ethyl acetate. The combined organic layers were washed with HCl (10% solution), brine, and dried (MgSO4), filtered, and concentrated under reduce pressure to give 415 mg (4-hexylphenyl)boronic acid as a colorless solid. A solution of the resulting boronic acid (962 mg, 4.07 mmol) and Intermediate 3 (1.1 g, 4.27 mmol) in toluene (37 mL), methanol (1.2 mL) and water (2 mL) were added potassium carbonate (1.09 g, 8.45 mmol) and LiCl (181 mg, 4.27 mmol) with stirring. After bubbling with Ar for 10 min, tetrakis(triphenylphosphine)palladium(0) (99 mg) was added and heated at 95° C. for 16 h. After the reaction mixture was cooled at RT, it was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, and dried (MgSO4), filtered, and concentrated under reduce pressure. The residue was purified by MPLC (15% ethyl acetate in hexanes) gave 1.16 g of Intermediate 6 as colorless solid. The reaction mixture was warmed at RT over 2 h After stirring at RT for 15 min the reaction mixture was quenched with saturated solution of ammonium chloride extracted with ethyl acetate The combined organic layers were washed with HCl (10% solution), brine dried (MgSO4) filtered concentrated

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 6.6 g (30.17 mmol) of 9, 7.28 g (30.17 mmol) of 1-bromo-4-hexylbenzene, 21.63 g (66.39 mmol) of caesium carbonate, 78 mg (0.3 mmol) of bis(acetonitrile)palladium(II) chloride and 431 mg (0.9 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl are dissolved in 90 ml of dioxane under nitrogen and heated at 100° C. overnight. 100 ml of water are added to the cooled solution, and the mixture is extracted twice with methyl t-butyl ether (100 ml). The combined organic phases are washed with water, dried over sodium sulfate and evaporated in vacuo. The residue is purified by column chromatography. the mixture is extracted twice with methyl t-butyl ether (100 ml) The combined organic phases are washed with water dried over sodium sulfate evaporated in vacuo The residue is purified by column chromatography