4-Bromo-N,N- diphenylaniline

White powder or crystal

Compound 1 wassynthesized by following reported procedures withslight modifications.23, 24 To a solution of triphenylamine(2.1 g, 8.16 mmol) in 40mL CCl4, NBS (1.6g, 8.16 mmol) was added and the reaction mixture refluxed for 4 h under nitrogen (N2) atmosphere. Duringthe reaction solid was formed which, conformed as succinimide.After filter the reaction mixture filtrate wasevaporated and recrystalized from ethanol. Yield 93percent.Triphenylamine 3 (12.25 g, 50 mmol) and NBS (9.0 g, 50 mmol) were dissolved in 200 mL carbon tetrachloride. The solution was refluxed for 4 h. The precipitated succinimide was filtered, and the solvent was evaporated from the solution. The remaining gray oil was recrystallized from ethanol. The obtained white crystalline powder (14.4 g, 89percent) was dried in a vacuum. Mp 102.6 °C, MS (EI): 323, 325. In the dark condition, 10.68g NBS was dissolved in carbon tetrachloride solution, 14.70g triphenylamine was added and refluxed at 80 ° C for 4 hours. The reaction was complete and the crude product was obtained. The crude product was recrystallized from ethanol to give pure intermediate 1 as a white powdery crystal in a yield of 85.0percentIn a three-necked, oven-dried, 150 mL round-bottom flask, triphenylamine (3.000 g, 12.244 mmol) was dissolved in50 mL of anhydrous chloroform, covered with aluminumfoil, and stirred at 25 °C under inert atmosphere for15 min. N-Bromosuccinimide (1.96 g, 11.121 mmol) wasthen added in small portions, and the resulting solutionwas stirred at 25 °C for 5 h. The reaction mixturewas extracted three times with chloroform. The combinedorganic fractions were washed with brine and driedover anhydrous MgSO4. The solvent was removed underreduced pressure and the residue was re-crystallized byusing ethanol to give a white powder (3.020 g, 76percent).1H NMR (300 MHz, CDCl3: 7.62–7.21 (m, 7H), 7.19–7.00 (m, 5H), 6.99–6.93 (m, 2H).2.3.3.7 35.6 g (200 mmol) of N-bromosuccinimide (NBS) was added into 1.5 L of ethyl acetate solution of 54.0 g (220 mmol) of triphenylamine, and stirred overnight. Then, the solution was concentrated to 1 L, and washed with 1 L of 5 percent sodium acetate EPO Step 1: Synthesis of 4-bromotriphenylamine] [0613]A synthetic scheme of 4-bromotriphenylamine in Step 1 is shown in the following (O- 1). [0614]NBS, Ethyl acetate (0-1) To 1.5 L of an ethyl acetate solution containing 54.0 g (220 mmol) of triphenylamine, 35.6 g (200 mmol) of λT-bromo succinimide (abbreviation: NBS) was added. Then, the mixture was stirred for 24 hours. After the obtained suspension was concentrated to 1 L, the concentrated suspension was washed with 1 L of an aqueous solution containing 5 percent of sodium acetate. After the washing, this solution was further concentrated to about 50 mL. Then, methanol was added to the concentrated solution and the solution was precipitated. The obtained precipitate was filtered and dried to obtain 46.5 g of an objective white powder at a yield of 73 percent.To 1.5 L of an ethyl acetate solution containing 54.0 g (220 mmol) of triphenylamine, 35.6 g (200 mmol) of JV-Bromosuccinimide (abbreviation: NBS) was added. After that, this mixture was stirred for 24 hours. After the obtained suspension was concentrated to 1 L, the concentrated suspension was washed with 1 L of an aqueous solution containing 5 percent of sodium acetate. After the washing, this solution was further concentrated to about 50 mL. Then, methanol was added to the concentrated solution and the solution was precipitated. The obtained precipitate was filtered and dried to obtain 46.5 g of an objective white powder at a yield of 73 percent. A synthetic scheme of Step 1 is shown in (b-3) given below.Hereinafter, a method for synthesis of N-(4-diphenylamino)phenylaniline by the synthesis method according to the present invention is explained, formula 1/T\A method for synthesis of N-(4-diphenylamino)phenylaniline represented by the structural formula 1 is explained, formula 2BrNBS(A-D ethylacetateAccording to the foregoing reaction scheme (A-l), N, N-diphenyl-N-(4-bromophenyl)amine was firstly synthesized. Triphenylamine (25.19 g, 0.102 mol), N- bromosuccinimide (18.05 g, 0.102 mol), and ethyl acetate (400 ml) were added to a 1000 ml Erlenmyer flask and the solution was stirred at room temperature in the air all night. After the reaction, the reacted solution was washed with saturated sodium carbonate twice to extract a water layer with ethyl acetate twice. The water layer and an organic layer were washed with saturated salt solution. After drying the organic layer with magnesium sulfate, the organic layer was filtered naturally and condensed to give colorless solid. The colorless solid was recrystallized with ethyl acetate-hexane and 22.01 g of colorless powder solid was obtained in a yield of 66percent. ^-NMR of the white powder solid was carried out to confirm that the white powder solid was N, N-diphenyl-N-(4-bromophenyl)amine and the result was asfollows:[Step 1: Synthesis Method of N, N, N'-triphenyl-1, 4-phenylenediamine (hereinafter, referred to as DPA)] Step 2: Synthesis of N, N, N'-triphenyl-1, 4-phenylenediamine (abbreviation: DPA In Step 2, DPA was synthesized according to (i) and (ii) shown below.; (i) Synthesis of 4-bromotriphenylamine; First, 25 g (100 mmol) of triphenylamine, 18 g (100 mmol) of N-bromosuccinimide, and 400 mL of ethyl acetate were put in a 1000-mL Erlenmeyer flask, and the mixture was stirred at room temperature in the air for 18 hours. After the reaction was terminated, the mixture was washed with a saturated sodium carbonate aqueous solution twice to obtain an organic layer and a water layer. Then, the water layer was extracted twice with ethyl acetate, and the extract was combined with the organic layer and washed with a saturated saline solution. The solution was dried with magnesium sulfate and filtered naturally, and the filtrate was concentrated. An obtained colorless solid was recrystallized with ethyl acetate-hexane; thus, 22 g of a colorless powdered solid of 4-bromotriphenylamine was obtained (yield: 66percent).25.19 g (0.102 mol) of triphenylamine, 18.05 g (0.102 mol) ofJV-bromosuccimmide, and 400 mL of ethyl acetate were put in a 1000 mL Erlenmeyer flask, and were stirred for about 12 hours at room temperature in the air. After the reaction was complete, an organic layer was washed twice with a saturated sodium carbonate solution. Then, an aqueous layer was extracted twice with ethyl acetate, combined with the organic layer, and washed with saturated saline solution. The solution was dried with magnesium sulfate, naturally filtered and concentrated, and a colorless solid was obtained. The solid was recrystallized with ethyl acetate and hexane, and 22.01 g of a colorless powdered solid was obtained, in a yield of 66percent. It was confirmed that this colorless powdered solid was 4-bromotriphenylamine by a nuclear magnetic resonance method (NMR). The measurement results according to a nuclear magnetic resonance method (NMR) are shown below.[0278] [Step 3] In a 1-L Erlenmeyer flask, 25 g (100 mmol) of triphenylamine, 18 g (100 mmol) of N-bromosuccinimide, and 400 mL of ethyl acetate were put and stirred at room temperature in air for 24 hours. After the reaction, the reaction solution was washed twice with a saturated aqueous solution of sodium carbonate to separate into an aqueous layer and an organic layer. The aqueous layer was extracted twice with ethyl acetate and washed with saturated saline together with the organic layer. After the organic layer was dried with magnesium sulfate, natural filtration and enrichment was performed, and the resulting white solid was recrystallized with ethyl acetate and hexane, whereby 22 g of a white powder solid of 4-bromotriphenylamine was obtained at a yield of 66percent.To 1000ml Erlenmeyer flasks, triphenylamine 25.19 g (0.102mol), N- bromosuccinimide 18.05g (0.102 mol), was placed ethyl acetate 400 ml, and stirred for about 12 hours at room temperature in air. After completion of the reaction, washing the organic layer twice with saturated aqueous sodium carbonate solution, the aqueous layer was extracted twice with ethyl acetate, washed with saturated saline together with the organic layer. After drying with magnesium sulfate, gravity filtered, and concentrated to a colorless solid with ethyl acetate thus obtained, to give a recrystallized place colorless powdery solid 22.01g, 66percent yield hexane. By a nuclear magnetic resonance method (1H-NMR), it was confirmed that this colorless powdery solid is 4-bromo-triphenylamine.Synthesis of 4-bromotriphenylamine Practical Example 6 Triphenylamine (5 g, 20.4 mmol) dissolved in toluene (24 mL) was added into the round bottom flask (100 mL, two-neck) and cooled in an ice bath. A solution of N-bromosuccinimide (4.35 g, 24.5 mmol) in DMF (12 mL) was added into the flask transfer through the addition funnel. After reacting for 15 min, the mixture was poured into cold water and extracted with CHA mixture of triphenylamine (20g, 81.5mmol) , NBS (17.4g, 97.8mmol) and CClWeighing triphenylamine (10.03g, 0.04mol), NBS (7.24g, 0.04mol) in a 250mL three-necked flask, adding 100mL of carbon tetrachloride as a solvent, vacuuming and purging the nitrogen repeatedly, stirring at room temperature for 1h, then heating up The reaction was refluxed to 80 °C. The reaction was monitored by TLC until the end.After removing the solvent, it was extracted with dichloromethane and dried over anhydrous sodium sulfate.After concentration, 11.47 g of 4-bromotriphenylamine as a white solid was obtainedExample 28e 1, 4-to [...] multi function cap opening 250 ml 2 (1, 4-dibromobenzene) (24.9 ml, 206.83mmol), diphenylamine (diphenylamine) (10.0g, 59.09mmol), tris (d it cuts qualitative the acetone which is burnt) d palladium (0) (Pd Is the starting material a diphenylamine (73.58g, 434.8mmol) senses a rotation velocity of the disk to a toluene in in round bottom flask , 1-bromo-4-iodobenzene (264.02g, 869.6mmol), Pd Compound I-1 (12.5 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (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-1 was obtained, With silicone as the stationary phase, Dichloromethane/hexane as eluent, The crude product is subjected to column chromatography.Compound III-1 (18.9 g, 79percent) was obtained.(1) Compound I-1 (21.85 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (20.88 g, 73.8 mmol), t-BuONa (10.7 g, 111 mmol), Pd(OAc)2 (0.33 g, 1.47 mmol)And ultrasonically deoxygenated toluene (1.5L), Return to liquid under nitrogen protection, After the reaction mixture was cooled, the mixture was treated with ethyl acetate and water, and the resulting organic layer was dried over MgSO 4 . The solvent was distilled off under reduced pressure to obtain a crude product of Compound III-1. The stationary phase was silica gel, and the dichloromethane/hexane was used as the stationary phase. The eluent, which was subjected to column chromatography, afforded compound III-1 (40.58 g, 78percent).Compound I-1 (12.5 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (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 MgSO 4 and the solvent was evaporated under reduced pressure.Obtained crude compound III-1 with silica gel as the stationary phase, The crude product was subjected to column chromatography with dichloromethane/hexane as eluent.Compound III-1 (18.7 g, 78percent) was obtained.(1) Compound I-1 (21.85 g, 73.8 mmol) and compound II-1 (20.88 g) were successively added to a round bottom flask.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) were refluxed under a nitrogen atmosphere until the reaction liquid was cooled. After treatment with ethyl acetate and water, the resulting organic layer was dried over MgSO 4 , and the solvent was distilled off under reduced pressure to obtain crude compound III-1.The crude product was subjected to column chromatography using silica gel as a stationary phase and dichloromethane/hexane as eluent to obtain compound III-1 (40.58 g, 78percent).Compound I-1 (12.5 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (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-1 was obtained, With silicone as the stationary phase, Dichloromethane/hexane as eluent, The crude product is subjected to column chromatography.Compound III-1 (18.7 g, 78percent) was obtained.(1) Compound I-1 (21.85 g, 73.8 mmol) was sequentially added to a round bottom flask. Compound II-1 (20.88 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), Return to liquid under nitrogen protection, 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-1. With silicone as the stationary phase, Dichloromethane/hexane as eluent, The crude product is subjected to column chromatography. Compound III-1 (40.58 g, 78percent) was obtained.Compound I-1 (12.5 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (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), 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.The crude product of compound III-1 was obtained using silica gel as stationary phase and dichloromethane/hexane as eluent.The crude product was subjected to column chromatography to give Compound III-1 (18.7 g, 78percent).(1) Compound I-1 (21.85 g, 73.8 mmol) was sequentially added to a round bottom flask.Compound II-1 (20.88 g, 73.8 mmol), t-BuONa (10.7g, 111mmol), Pd(OAc) 2 (0.33 g, 1.47 mmol) and ultrasonic deoxygenated toluene(1.5 L), the mixture was refluxed under a nitrogen atmosphere. After the reaction mixture was cooled, ethyl acetate and water were evaporated.Obtaining the crude product of compound III-1 with silica gel as the stationary phase.The crude product was subjected to column chromatography eluting with methylene chloride/hexane to afford compound III-1 (40.58 g, 78percent).To a round bottom flask Sub 1-2-1-1 (5.7g, 20mmol), Sub 1-2-2-1 (3.4g, 20mmol), pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g , 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL)The reaction proceeds at 100 after loading. After completion of reaction, the organic layer was dried over MgSO4, and extracted with water and ether and the organics concentrated and generating silicagel column and recrystallized Sub 1-2-3-1 4.9g (yield: 76percent) was obtainedThe M 1-1 (45.05 g, 266.2 mmol) to a round bottom flask was charged with toluene (2000 ml) to dissolve after, 1-bromo-4-iodobenzene (150.63 g, 532.4 mmol), Pd2(dba)3 (7.31 g, 8 mmol), was 50percent P(t-Bu)3 (10.4 ml, was added to 21.3 mmol), NaOt-Bu (76.76 g, 798.7 mmol) and stirred at 70°C. After the reaction was completed CH2Cl2. And extracted with water, the organic layer was dried with MgSO4 and concentrated to produce the compound and then a silicagel column and the product was recrystallized from 63.01 g (yield: 73percent) was obtained.L round bottom flask formula diphenyl amine 20 g (118 mmol), 1- bromo-4-iodo-benzene 33.4 g (118mmol), potassium hydroxide 13.2 g (236 mmol) the mixture was stirred into 400 ml of xylene. 1, 10 nansseu page in five minutesAnd stirred to give after adding a rolrin gave 7 g (35.5 mmol). If the materials are somewhat rust Cooper iodide 6.75 g(35.5 mmol) was added raising the temperature back to the mixture was heated under reflux for 18 hours. Using ethyl acetate and water to the impuritiesGave was removed after the removal of water into the anhydrous magnesium sulfate. The filter is then the solution of ethyl acetate and ethanolUsing recrystallization to give the formula M 2-1 24 g (63percent)A solution of CuI (6.7 mg, 0.035 mmol), NaO

Molecular Weight:324.2
XLogP3:6.4
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:3
Exact Mass:323.03096
Monoisotopic Mass:323.03096
Topological Polar Surface Area:3.2
Heavy Atom Count:20
Complexity:255
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes