N-(4-Bromophenyl)-[1,1'-biphenyl]-4-amine

Step 1: Synthesis of 4-bromo-4'-phenyl-diphenylamine][0803]A synthetic scheme of 4-bromo-4'-phenyl-diphenylamine in Step 1 is shown in the following (V-I). [0804][0805]After 37 g (150 mmol) of 4-phenyl-diphenylamine was dissolved in 400 mL of ethyl acetate in a 1000-mL conical flask, 27 g (150 mmol) of JV-bromo succinimide (abbreviation: NBS) was added to this solution. After that, this mixture was stirred at room temperature for 24 hours. [0806]After completion of the reaction, this mixture solution was washed with water, and magnesium sulfate was added thereto to remove moisture. This mixture solution was filtrated through Florisil, silica gel, alumina, and then Celite, the obtained filtrate was concentrated, and toluene and hexane were added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain 4.0 g of an objective white In a stream of nitrogen, a 100 mL three-necked flask was charged with 15.0 g (61.1 mmol) of N-phenyl-Nbiphenylylamine.100 mL of dimethylformamide and 10.8 g (61.1 mmol) of N-bromosuccinimide were added to thecontent, and the mixture was stirred at room temperature for 2 hours. To the thus-obtained reaction mixture, 10 mL oftoluene and then 10 mL of pure water were added, and the reaction mixture was separated into an organic phase andan aqueous phase. The organic phase was washed with pure water and then with an aqueous saturated sodium chloridesolution. The washed organic phase was dried over anhydrous magnesium sulfate, and then, the solvent was distilledoff under reduced pressure. The thus-obtained solid was recrystallized from toluene to give 13.4 g (41.4 mmol) of N-(4-bromophenyl)-N-biphenylylamine as a grey powder (yield: 67percent). The compound was identified by 1H-NMR measurement and 13C-NMR measurement. 1H-NMR(Acetone-d6); 7.55-7.64(m, 5H), 7.27-7.45(m, 5H), 7.21(d, 2H), 7.11(d, 2H) 13C-NMR(Acetone-d6); 143.18, 142.61, 140.76, 133.40, 132.08, 128.88, 127.74126.62, 126.26, 118.90, 118.05, 111.33Under argon atmosphere, into a mixture of 32.4 g (100.0 mmol) of 31 g (95.62 mmol) of M-2 and 24.7 g (143.43 mmol) of naphthalen-1-ylboronic acid were placed in a round bottom flask, and 400 ml of toluene was added thereto to dissolve it, and it was added thereto. A 250 ml aqueous solution obtained by dissolving 39.65 g (286.85 mmol) of potassium carbonate was stirred and the mixture was stirred. Subsequently, 2.21 g (1.91 mmol) of tetratriphenylphosphine palladium was added thereto, and the obtained mixture was refluxed under a nitrogen atmosphere and stirred for 12 hours. When the reaction was completed, the resultant was extracted with dichloromethane and distilled water, the extracted solution was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by hydrazine column chromatography using n-hexane/dichloromethane (7:3 vol/vol) to obtain 31.3 g of intermediate M-3 (yield 88%).N- (4-bromophenyl) - [1, 1'-biphenyl] -4-amine (3 g, 9.29 mmol)Triphenylene-2-Ylboronic acid (2.53 g, 9.29 mmol), And 2 mol% of tetrakis (triphenylphosphine) palladium were added to tetrahydrofuran (20 ml), potassium carbonate (18.58 mmol)Were dissolved in water (10 ml) and mixed.After stirring at 80 C for 6 hours, the reaction was terminated and the reaction mixture was cooled to room temperature to separate the water and the organic layer. After recovering only the organic layer, anhydrous magnesium sulfate was added and stirred, The mixture was filtered through a silica pad, concentrated under reduced pressure, and purified by column to obtain Intermediate 4-1 (3.54 g, yield 81%).N-(4-bromophenol-4-biphenylamine (9.7 g, 30 mmol, 1 eq.), P3Bpin (10.7 g, 1 eq.), sodium carbonate (9.5 g, 3.0 eq.), and tetrakis(triphenylphosphine) palladium(0) (1.04 g, 0.03 eq.) were weighed and put into a 1 L three-necked round bottom flask. Degassing under reduced pressure and nitrogen purge were sufficiently performed. Thereafter, toluene (80 mL), ethanol (20 mL), and water (20 mL) were added thereto in a nitrogen atmosphere, and the mixture was refluxed and stirred. After completion of the reaction, heating was stopped, and the temperature of the reaction liquid was returned to room temperature. Extraction was performed with toluene, the organic solvent layers were then unified, anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand for a while. Sodium sulfate was filtered off, and the solution was concentrated under reduced pressure. The resulting mixture containing a desired product was caused to pass through a silica gel short column chromatography, and a fraction containing a desired product was collected and concentrated under reduced pressure. The mixture containing a desired product was further caused to pass through a silica gel column chromatography, and a fraction containing a desired product was collected and concentrated under reduced pressure. Thus, a desired product ' P2NP4' was obtained.The intermediate O and 26.1g 21.3g 4- bromo-4-phenyl-diphenylamine was added to a 1L three-necked flask, Add 500ml toluene and 120ml ethanol to dissolve, Pass nitrogen for 15 minutes, Then add 100ml K2CO3 (3.0eq., 2M) in water, mostAfterwards, 1.5 g of Pd(PPh3)4 (2 mol%) was added.Warm up to 110C, The reaction ended overnight.Cool to room temperatureAdd activated carbon adsorption, Suction filtrationSpin off the solvent, It was dried and recrystallized from toluene and ethanol to give 26.5 g of Intermediate P in a yield of 72%.0.342 g (1.00 mmol) of (biphenyl-4-yl) (4-bromophenyl) amine, 0.176 g (1.05 mmol) of 9H-carbazole, 4.6 mg (1.05 mmol) of tris (dibenzylideneacetone) dipalladium 5.0 mumol), 14.9 mg (35.0 mumol) of 2- (di-tert-butylphosphino) -2 ', 4', 6'-triisopropyl-1, 1'-biphenyl, After adding 0.144 g (1.50 mmol) of sodium tert-butoxide and 3 mL of o-xylene, the inside of the reaction system was replaced with argon gas. Thereafter, the mixture was heated to 140 C. and stirred for 15 hours.After cooling to room temperature, the reaction was stopped by adding 25 mL of water. Further, 20 mL of ethyl acetate and 3, 6-dibromo-9-phenyl-9H-carbazole as an internal standard were added and stirred until the ethyl acetate layer became homogeneous. 0.2 mL of the ethyl acetate layer was collected, diluted with 4 mL of tetrahydrofuran, HPLC analysis showed that the conversion of (biphenyl-4-yl) (4-bromophenyl) amine was 99% or more and 9- [4- Biphenyl-4-yl) aminophenyl] -9H-carbazole was produced in an amount of 97% based on (biphenyl-4-yl) (4-bromophenyl) amine.General procedure: Intermediate 3-1 (3.2 g, 0.010 mol) in 2-bromo-4 , 6-diphenyl-1 , 3, 5-triazine (3.1 g, 0.010 mol), Pd (dba) 2 (0.5 g, 0.0005 mol), sodium-tert-butoxide (1.9 g, 0.020 mol) in100 mL Tol and stirred for 4 hours at 95 C. After the reaction cooled toH20: After layer separation the MC column purification (n-Hexane: MC) to afford 4.3 g(yield 77%) of Intermediate Compound 3-2General procedure: 1, 4-dibromobenzene (2.4 g, 0.010 mol) in N-(biphenyl-4-yl) -9, 9-dimethyl-9H-fluoren-2-amine (3.6 g, 0.010 mol), Pd(dba)2 ( 0.5 g, 0.0005 mol), sodium-tert-butoxide (1.9 g, 0.020 mol) in 70 mL TOL into a 95C, 4 hours reaction was stirred. After completion of the reaction H 2 0: after the delamination MC column purification (n-HEXANE: MC) to afford 4.1 g of Intermediate 1-1 (79%). (M / z = 516)Synthesis Synthesis of N-biphenylyl-N-[4-(4-dibenzothienyl)phenyl]amine In a stream of nitrogen, a 300 mL three-necked flask was charged with 7.0 g (21.6 mmol) of

Molecular Weight:324.2
XLogP3:5.8
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:3
Exact Mass:323.03096
Monoisotopic Mass:323.03096
Topological Polar Surface Area:12
Heavy Atom Count:20
Complexity:271
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes