4,4''-Dibromo-p-terphenyl

White to light yellow solid

100 g of terphenyl and 1 L of bromobenzene were placed in a 2 L reaction flask, and 174 g of liquid bromine was added thereto with stirring, and the mixture was further heated to 110 ° C for 40 hours.At least a portion of the Br2 vapor produced by heating the terphenyl and liquid bromine is condensed back to the reaction flask using low temperature (-10-0 °C) condensation, and at least a portion of the Br2 and hydrogen bromide vapor are absorbed using water.After cooling to 25 ° C, the reaction solution of terphenyl and liquid bromine was poured into 2 L of methanol, stirred for 0.5 hours, filtered, and the filter cake was washed at least once with 800 mL of methanol.The filtered cake was dried in a forced air oven at 60 ° C for 2 hours.The dried crude product was added to 200 mL of toluene and refluxed for 12 hours. After hot filtration, the filter cake was rinsed once with 200 mL of toluene and then drained.The dried filter cake was further added to 200 mL of toluene and refluxed for 4 hours. After hot filtration, the filter cake was rinsed once with 200 mL of toluene.Drain.The obtained filter cake was placed in a blast oven and dried at 80 ° C for 24 hours to obtain 119 g of a white solid.The product was 4, 4'-dibromo-p-terphenyl, and the yield was 70.6percent.In a 2 L 3-necked flask equipped with a thermometer, mechanical stirrer, reflux condenser and scrubber was placed 1.6 L of trichlorobenzene. To this was added 100 g of p-terphenyl and 100 mg of iodine. This mixture was stirred for 10 minutes at a temperature of roughly 22° C., after which 45 mL of bromine was added. The mixture was next heated at about 100° C. for 1 hour, while being stirred. The mixture was then cooled, and methanol was added to trigger precipitation. The precipitate was collected by filtration and washed with methanol. Finally, the product was dried under vacuum to give a white powder in 69percent yield.(1) The charged contents were heated, refluxed for 2 hours by stirring, and allowed to cool to prepare a reaction liquid. Then, methanol was added to the reaction liquid, and the resulting precipitate was collected by filtration. The precipitate was dissolved by heating in chlorobenzene, and the solution was subjected to adsorption purification using silica gel. Then, adsorption purification using activated clay was performed whereafier crystallization using a chlorobenzene/ methanol mixed solvent was carried out. Then, reflux cleaning using methanol was performed. As a result, 16.25 g (yield 90percent) of Compound 1-34 was obtained as a white powdet.For the resulting white powder, its structure wasidentified using NMR. In 'H-NMR (CDC13), the followingsignals of 48 hydrogens were detected.oe (ppm)=7.84 (1H)7.70-7.03 (35H)1.48 (12H)STEP 2: Synthesis of N4, N4-di([1, 1'-biphenyl]-4-yl)-N4, N4-bis(3-fluoro-4-methylphenyl)-[1, 1':4', 1-terphenyl]-4, 4-diamine 4, 4-Dibromo-1, 1':4', 1-terphenyl (7.33 g, 18.9 mmol), N-(3-Fluoro-4-methylphenyl)-[1, 1'-biphenyl]-4-amine (11.0 g, 39.7 mmol, 2.16 eq.), Pd(dba)2 (217 mg, 0.57 mmol, 2.0 mol percent), PtBu3 (115 mg, 0.57 mmol, 2.0 mol percent), and KOtBu (6.36 g, 56.7 mmol, 3.0 eq.), were charged in a flask under nitrogen atmosphere. The solids were suspended in anhydrous toluene, and the suspension was refluxed for 22 h at 80° C. After cooling to room temperature, it was filtered over silica, the pad was abundantly rinsed with tetrahydrofuran, and the filtrate was evaporated to dryness. The resulting solid was triturated in refluxing methanol (150 mL) for 20 min, and the suspension filtered hot, yielding after drying 14.9 g of the title compound (98.9percent yield) with 98.92percent purity according to HPLC. The product was then sublimed to yield yellow amorphous solid with 99.51percent purity according to HPLC. Elemental analysis: C 85.88percent (86.13percent theor.), H 5.60percent (5.42percent theor.) N 3.61percent (3.59percent theor.) Glass Transition Onset: Tg=114° C. (from DSC 10 K/min), no melting peak observed.(0053) Elemental analysis: C 85.88percent (86.13percent theor.), H 5.60percent (5.42percent theor.) N 3.61percent (3.59percent theor.) (0054) Glass Transition Onset: Tg=114° C. (from DSC 10 K/min), no melting peak observed.