BIS(4-BROMOPHENYL)AMINE

Off-white powder

To a magnetically stirred solution of diphenylamine (17.0 g., 0.1 mol.), in dimethylformamide (100 ml), at 10 C., N-bromosuccinimide (35.5 g., 0.2 moles) was added in portions, keeping temperature below 20 C. The mixture was stirred at room temperature for 18 hours and then poured into 1000 ml of water. The oil that first separated, solidified on stirring to leave 32 g., of solids. Recrystallization from hexanes gave 4, 4'-dibromodiphenylamine, m.p. 105-107 C., 18, 8 g., 60% yield.[Step 1] A synthesis method of N, N-4, 4'-dibromodiphenylamine Diphenylamine (39.8 g, 0.235 mol) was charged into a flask containing DMSO (200 mL) and allowed to dissolve. HBr (48% aqueous, 150.0 mL, 1.33 mol) was added dropwise resulting in a cloudy white mixture, which was stirred overnight whereby a white solid precipitated. The solid was collected by vacuum filtration and washed with DI water (3*50 mL) followed by recrystallization from hexanes to yield white crystalline needles, Purity: 99+% (GC).5 g (29.6 mmol) of diphenylamine was weighed into a 250 ml three-necked flask, 50 ml of dimethylformamide (DMF) as a solvent, Magnetic stirring and through the argon, Ice salt bath conditions for 30min, weighed 59. 2mmol (10. 53g) Bromosuccinimide (NBS) was added and dissolved in 50 ml of DMF, Was added dropwise to the three-necked flask and added dropwise over 30 minutes, The reaction was carried out under ice-salt bath for 6 h. After the reaction is finished, pour the reaction solution into the ice brine and vigorously stir and precipitate the gray solid, Filtered and washed three times with saturated sodium bicarbonate (NaHC03) solution, Drying in vacuo at 60 & lt; 0 & gt; C overnight yielded 8. 8 g of product, Yield 91%. The chemical formula of the intermediate is C12H9NBr2, the molecular weight is 327. 01, Its structure is as follows:According to a literature procedure, 25 Ph2NH (6, 60.00 g, 354.56 mmol) was dissolved in DMF (200 mL) and cooled to 0 C. Under vigorous stirring, a solution NBS (126.88 g, 712. mmol, 2.01 equiv) in DMF (400 mL) was added dropwise and the mixture was stirred at r.t. for 48 h. Then, the mixture was poured into H2O (1.5 L) and the resulting precipitate was filtered. The solid was recrystallized (EtOH/H2O) to give the product (Figure 8) as colorless crystals; yield: 89.77 g (274.5 mmol, 77%); mp 107.5 C. Analytical data match data reported in the literature.25 1H NMR (CDCl3, 500 MHz, 300 K): delta = 5.624 (br, N-H), 6.915 (d, 4 H, 2-H), 7.362 (d, 4 H, 3-H). 3J2, 3 = 8.70 Hz. MS (EI): m/z (%) = 327 (100, [M]+]), 247 (10, [M - Br]+), 167 (50, [M - 2Br2]+). Anal. Calcd for C12H9Br2N: C, 44.07; H, 2.77; N, 4.28. Found: C, 44.10; H, 2.82; N, 4.32.[3-1] Synthesis of 4-bromodiphenylamine In a 1000-mL Erlenmeyer flask were placed 20 g (118.1 mmol) of diphenylamine, 500 mL of chloroform, and an ellipsoidal stirring chip. In a 500-mL beaker was placed 113.8 g (236.2 mmol) of tetrabutylammoniumtribromide (TBABr3), which was dissolved in 200 mL of chloroform added later. The resulting solution was added dropwise to the chloroform-diphenylamine solution, and the mixture was stirred for 20 hours at room temperature in the air. Then, the chloroform-diphenylamine solution was transferred to a 1000-mL separatory funnel and washed seven times with 100 mL of saturated aqueous solution of sodium thiosulfate. The organic layer was transferred to a 1000-mL Erlenmeyer flask and then dehydrated with 100 g of anhydrous magnesium sulfate. With the anhydrous magnesium sulfate removed by filtration, the chloroform solution was transferred to a 1000-mL eggplant-shaped flask and freed of chloroform by means of an evaporator. The resulting crude product was purified by means of a silica gel column (hexane:chloroform = 1:1) (Yields: 70%). 1H-NMR;delta 5.8 (-NH, 1H, s), 7.0-7.6 (Ar, 8H, d) ppmDiphenylamine 40 g (236 mmol) was dissolved in 400 mL dimethylformamide and the mixture was stirredat 0 . Then N- bromosuccinimide 82 g (461 mmol) is added slowlyto the reactor. After raising to room temperature the mixture was stirred for 4hours. When the reaction is completed distilledwater was added dropwise at room temperature to form brown crystals and thecrystals were filtered and then recrystallized with toluene and methanol togive 40 g of compound represented by the . (Yield 60%)(14.7 g, 87.9 mmol) and 150 ml of dichloromethane are placed in a 1 L round bottom flask reactor and stirred. Bromine (2.5 g, 102 mmol) was slowly added dropwise at room temperature and stirred for 5 hours. After completion of the reaction, precipitation was carried out using methanol to obtain (17.1 g, 82%). (40 g, 60%) was obtained using the same method except that diphenylamine was used instead of in Synthesis Example 3-4.A 1 L reactor was charged with 40 g (236 mmol) of diphenylamine in dimethylformamideAnd the mixture was stirred at 0 C. N-bromosuccinimide 82 g (461 mmol)Was slowly added to the reactor, and the mixture was stirred at room temperature for 4 hours.After completion of the reaction, H 2 O was added dropwise at room temperature, followed by filtration when brown crystals were formed And recrystallized with toluene and methanol to obtain 40 g of [intermediate 8-a]. (Yield: 60%)Diphenylamine g 10 (59 mmol) of N- ethyl acetate solution (400 mL) containing bromo succinic imide Mo 22.1 g (124 mmol) of, Which was stirred at room temperature for 16 hours. After the reaction, the reaction mixture was washed with water, and add the award with ethyl acetateEx, and the extract solution was mixed with the organic phase. After washing the resultant organic phase with a saturated sodium chloride solution, the organic phase sulfate MargDried with magnesium. Then, the mixture was suction filtered, and the filtrate was concentrated. The resulting residue was washed with hexaneAnd, as a result of suction filtration to recover the solid the hexane suspension, the target product, N, N- bis (4-bromophenyl) amine 9.5 g (yield:To give a 49%) as a white solid.N-bromosuccinimide (17.8 g, 0.1 mol) in 50 mL of DMF was added slowly to diphenylamine (8.46 g, 0.05 mol) in 50 mL of DMF at 0 C. in 30 minutes. The reaction was allowed to warm to room temperature and stir overnight. The white precipitate was filtered and air dried, and 16 g of product was collected.

Molecular Weight:327.01
XLogP3:4.8
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:326.90813
Monoisotopic Mass:324.91017
Topological Polar Surface Area:12
Heavy Atom Count:15
Complexity:162
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes