N-(4-BroMophenyl)-N,N-bis(1,1'-biphenyl-4-yl)aMine

Compound I-2 (23.7 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-2 (20.9 g, 73.8 mmol), t-BuONa (10.7 g, 111 mmol), Pd(OAc)2 (0.33 g, 1.47 mmol) and ultrasonically deoxygenated toluene (1.5 L), Reflux overnight under nitrogen, After the reaction solution was cooled, treated with ethyl acetate and water, The resulting organic layer was dried over MgSO4.The solvent was distilled off under reduced pressure to give a crude product of compound III-2.Silica gel as stationary phase, dichloromethane/hexane as eluent, The crude product was subjected to column chromatography to give Compound III-2 (28.8 g, 82percent)Compound I-3 (23.7 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-3 (20.9 g, 73.8 mmol), t-BuONa (10.7 g, 111 mmol), Pd(OAc)2 (0.33 g, 1.47 mmol) and ultrasonically deoxygenated toluene (1.5 L), Reflux overnight under nitrogen, After the reaction solution was cooled, treated with ethyl acetate and water, The resulting organic layer was dried over MgSO4.Evaporate the solvent under reduced pressureThe crude compound III-3 was obtained, With silicone as the stationary phase, Dichloromethane/hexane as eluent, The crude product is subjected to column chromatography.Compound III-3 (28.8 g, 82percent) was obtained.Compound I-2 (23.7 g, 73.8 mmol), compound II-2 (20.9 g, 73.8 mmol) were sequentially added to a round bottom flask.t-BuONa (10.7 g, 111 mmol), Pd(OAc) 2 (0.33 g, 1.47 mmol), and ultrasonically deoxygenated toluene (1.5 L), After refluxing under nitrogen, the reaction solution was cooled and treated with ethyl acetate and water.The resulting organic layer was dried over MgSO 4 and the solvent was evaporated under reduced pressure.Obtained crude product of compound III-2 with silica gel as the stationary phase, Column chromatography of the crude product with dichloromethane/hexane as eluent afforded compound III-2 (28.8 g, 82percent).Compound B-6 (39.04 g, 138 mmol) was added to the reaction vessel in that order.Compound F-6 (40.34g, 125.5 mmol), Pd2 (dba) 3 (5.74 g, 6.3 mmol), P(t-Bu)3 (2.54g, 12.5mmol), After NaOt-Bu (36.2 g, 376.4 mmol) and toluene 1500 mL, the reaction was carried out at 100 ° C.After the reaction, the organic matter is extracted with diethyl ether and water.The organic layer was dried over magnesium sulfate and then concentrated to afford compound C-6 (47.83 g, 80percent).Synthesis of Intermediate 3; 8.5 g (30 mmol) of 4-bromoiodobenzene, 6.45 g (20 mmol) of Intermediate 2, 4.3 g (45 mmol) of t-BuONa, 0.55 g (0.6 mmol) of Pd2(dba)3, and 0.12 g (0.6 mmol) of P(t-Bu)3 were dissolved in 100 mL of toluene and stirred at 90°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted three times with distilled water and 100 ml of diethylether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 7.53 g (yield: 79percent) of Intermediate 3.Add 32.1 g (100 mmol, 1.0 eq.) to a dry 1 L three-necked flask.Bis(4-biphenyl)amine and 56.4 g (200 mmol, 2.0 eq.) of p-bromoiodobenzene, Add 500 ml of toluene and stir to dissolve, and add 11.5 g (120 mmol, 1.2 eq) of sodium tert-butoxide.With nitrogen for 15 minutes, 0.9 g (1 mmol, 0.01 eq) of tris(dibenzylideneacetone)dipalladium was added.Add 4 ml (2 mmol, 0.02 eq) of a solution of tri-tert-butylphosphine in toluene (10percent), Nitrogen protection, heating to 60 ° C, reaction for 3 hours, the reaction is completed.Cool to room temperature, suction filtration, wash the filter cake with water, wash the filter cake with ethanol, and beat it with ethanol 3 times.The filter cake was recrystallized from toluene to give 37.0 g of Intermediate-5, yield 78percent.4-bromo-iodobenzene (3.4g, 12 mmol), bis-diphenyl-amine (3.86g, 12 mmol) was dissolved in N, N- dimethylacetamide and 50ml, copper chloride (CuCl) (164 mg, 1.2 mmol), followed by the addition of 2, 2'- bipyridyl (187 mg, 1.2 mmol), and reflux was conducted in a nitrogen atmosphere for 12 hours. After cooling to room temperature, distilled water (200mL) added to the reaction solution to complete the reaction, it is extracted with with chloroform (3 x 100 mL). The organic layer was dried over magnesium sulfate, and distilled under reduced pressure. The product was recrystallized from ethyl ether and hexane to prepare the Formula B-1 (3.7g, 65percent).After introducing 10 g of compound B (31 mmol), 13.2 g of 1-bromo-4-iodobenzene (46 mmol), 855 mg of tris(dibenzylideneacetone)dipalladium(0) (0.9 mmol), 757 mg of tri(o-tolyl)phosphine (2.5 mmol), 6 g of sodium tert-butoxide (62 mmol), and 310 mL of toluene into a reaction vessel, the mixture was stirred for 4 hours at 120. After completion of the reaction, the reaction product was cooled to room temperature, and then was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Thereafter, the resulting product was purified by column chromatography to obtain 7 g of compound 2-1 (47 percent).Inthe above [Reaction formula 11] displayed as is obtained fromcompound 7.9 g (24.6 mmol), 4-bromo iodobenzene8.3 g (30 mmol), Palladium acetate 0.4 g(0.3 mmol), sodium tertButoxide 4.2 g (43 mmol), tri-tertbutyl phosphine 0.1 g(0.3 mmol) and, 100 ml of toluene is stirred under reflux for 13 hours. Thefiltrate is concentrated after the completion of the reaction by filtration. Itis separated by column chromatography and recrystallized with methylenechloride and methanol to obtained 4.0 g of the compound represented by. (Yield 45percent)In a 250 ml reactor, 7.9 g (24.6 mmol) of [Intermediate 8-b]8.3 g (30 mmol) of 4-bromoiodobenzene, 0.4 g (0.3 mmol) of palladium acetate, 4.2 g (43 mmol) of sodium tertiary butoxide, 0.1 g (0.3 mmol) of tri-tert-butylphosphine, 100 ml of toluene was added and the mixture was refluxed and stirred for 13 hours.After completion of the reaction, the reaction mixture was filtrated, and the filtrate was concentrated and separated by column chromatography 4.0 g of [Intermediate 8-c] was obtained. (Yield: 45percent).In a 250 ml reactor, (7.9 g, 24.6 mmol), 4-bromoiodobenzene (8.3 g, 30 mmol)Palladium acetate (0.4 g, 0.3 mmol), Sodium tertiary butoxide (4.2 g, 43 mmol), Tertiary butyl phosphine (0.1 g, 0.3 mmol), 100 ml of toluene was added and the mixture was stirred under reflux for 13 hours.After completion of the reaction, the filtrate is concentrated and the filtrate is concentrated. The reaction mixture was separated by column chromatography to obtain (4.0 g, 34percent).Di([1, 1′-biphenyl]-4-yl)amine (3.5 g, 10.9 mmol) and 1-bromo-4-iodobenzene (6.0 g, 21.3 mmol) were mixed in 300 mL of dry toluene. The solution was bubbled with nitrogen while stirring for 15 minutes. Pd(OAc)Step 2: Synthesis of 4-bromo-4', 4-diphenyltriphenylamine] [0321] With the use of Step 1-1 and Step 1-2 which are described above, or4, 4'-diphenyltriphenylamine which was synthesized using a synthetic method shown in Step 1', 4-bromo-4', 4-diphenyltriphenylamine is synthesized. Note that a synthetic scheme of 4-bromo-4', 4-diphenyltriphenylamine in Step 2 is shown in the following (E-2). [0322](E-2) Under a nitrogen atmosphere, In a 1 L three-necked flask equipped with a stirrer, 33.0 g (83.0 mmol) of the compound (C-1), 150 mL of dichloromethane was added, and the mixture was stirred at room temperature for 5 minutes. To this solution, 14.8 g (83.2 mmol) of N-bromosuccinimide, was dissolved in 450 mL of dichloromethane, was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 5 hours. After completion of the reaction, 200 mL of pure water pure water was added to the reaction solution, and the mixture was washed and separated. Further, after washing and separation with saturated brine, the obtained organic layer was concentrated under reduced pressure and the solvent was distilled off. The obtained pale yellow powder was washed with hexane, white powder 34.3 g was obtained (yield 87percent, purity 97.9percent).Intermediate A 7-1 (1.0 eq) was dissolved in dichloromethane(10 times to Intermediate A7-1) and N-bromosuccinimide(1.05 eq) was slowly put into the round bottomflask for 10 min, and agitated for 4 hours. After 100 ml ofthe sodium thiosulfate aqueous solution was put and agitatedfor 20 min, the organic layer was separated. The separatedorganic layer was washed by 50 ml of the sodium chlorideaqueous solution and then dried by magnesium sulfateanhydride. The crude product was purified by colunm chromatographyon silica gel to give Intermediate A 7 with whitesolid, yield 75percent.N-bromosuccinimide (29 g, 162.9 mmol) in a 1 L round bottom flask, and the compound 1 (60 g, 150.9 mmol) was dissolved in 800 ml of chloroform and stirred for 4 hours.After adding 100 ml of aqueous sodium thiosulfate solution and stirring for 20 minutes, the organic layer was separated.The separated organic layer was washed with 50 ml of an aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The solution was filtered, concentrated under reduced pressure and recrystallized from chloroform and ethanol to obtain Compound 2 (54.4 g, 114.2 mmol) in a yield of 75.7percent4) Under a N2 protection, (88 mmol, 35 g) of N, N-bis(4-biphenyl)aniline was added to a 1000 mL three-necked flask.After 600 mL of dried chloroform, NBS (92.5 mmol, 16.46 g) was added slowly and stirred at room temperature overnight.The reaction solution was washed twice with 400 mL of water, dried over anhydrous magnesium sulfate, filtered and evaporated to dryness.Solid dry, Obtained 27.27 g, yield 70percent.4-bromine-aniline (10g, 58mmol) and 4-iodine biphenyl (34.2g, 122mmol), 1, 10-indoline trawl lung difficulty (2.3g, 11.6mmol), doesn't have any error frames, 150 ml xylene, 30 minutes in 80 °C heating stirring section. Copper most chloride herein (1.15g, 11.6mmol) and a of potassium hydroxide to form a solution (26.1g, 465mmol), added 50 ml xylene reflux the heating at a 15. Furthermore, 50 ml xylene reaction mixture using filtering the passing plates comprises a back plate supply unit BTS, for the concentration of filtrate was obtained. Silica gel column chromatography purified is citrus, 3 16.6g intermediate that is drying a obtained (yield 60percent). Derivatives, HR-MS, 4-bromo-aniline) (1.72 g, 10 mmol), 4-iodobiphenyl) (6.72 g, 24 mmol), potassium carbonate (K4-bromoaniline (4-bromo-aniline, 1.72g, 10mmol), 4-iodobiphenyl (4-iodobiphenyl, 6.72g, 24mmol), K2CO 3 (5.52g, 40mmol), copper iodide (CuI, 0.381g, 2mmol) and 1, 10-phenanthroline(1, 10-phenanthroline, 0.360g, 2mmol)were suspended in xylene (50mL) and refluxed under stirring for 24hours. After cooling to room temperature, the mixture was diluted withwater (100mL), and extracted with ethylacetate. The organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure, andre-crystallized with hexane to obtain compound B-23 (1.43 g, yield 30percent).

Molecular Weight:476.4
XLogP3:9.1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:5
Exact Mass:475.09356
Monoisotopic Mass:475.09356
Topological Polar Surface Area:3.2
Heavy Atom Count:32
Complexity:489
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes