| 91% |
With nitric acid; acetic acid at 110℃; |
|
| 91.4% |
With nitric acid; acetic acid at 100℃; for 0.5h; |
1 Synthesis of 1-nitro-4,4'-dibromobiphenyl
20 g (64 mmol) of 4,4'-dibromobiphenyl and 300 ml of glacial acetic acid was added to a 500 ml three-necked flask, heated to 100° C. with stirring, 100 ml 95% of fuming nitric acid was added dropwise, continued heating reaction for 30 min while maintaining the temperature at 100° C. After cooling and suction filtration, a yellow paste was obtained, which was recrystallized from ethanol to give 20.88 g of a yellow solid with a yield of 91.4%. 1HNMR (300 MHz, CDCl3) δ (ppm): 8.03 (d, J=1.8 Hz, 1H), 7.76 (dd, J=6.3 Hz, 2H), 7.56 (m, 2H), 7.3 (s, 1H), 7.16 (m, 2H). |
| 90% |
With nitric acid; acetic acid at 100℃; |
|
| 90% |
With nitric acid; acetic acid at 100℃; for 0.5h; |
|
| 88.72% |
With nitric acid; acetic acid at 100℃; for 1.5h; |
|
| 88% |
With nitric acid; acetic acid at 100℃; for 12h; |
2.2.9. 4,40-dibromo-2-nitrobiphenyl (7)
A solution of 4,40-dibromobiphenyl (5.0 g, 16.03 mmol) in 75 mLof glacial acetic acid was heated to 100 C, and then 60 mL of nitric acid was added dropwise. The solution was stirred at 100 C for12 h. After cooling to room temperature, the reaction mixture waspoured into an ice-water mixture. The precipitate was collected byfiltration, washed with excess of water, and purified by gel chromatography(silica gel, ethyl acetate/hexane 1/10 in volume ratioas the eluant) to give a yellow solid (5.03 g, 88%). 1H NMR (CDCl3,ppm): 7.14 (d, J 8.0 Hz, 1H, aromatic proton), 7.27 (d, J 8.0 Hz,1H, aromatic proton), 7.55 (d, J 8.0 Hz, 1H, aromatic proton), 7.74(dd, J1 8.0 Hz, J2 2.0 Hz, 1H, aromatic proton), 8.02 (d, J 2.0 Hz,1H, aromatic proton). 13C NMR (CDCl3, ppm): 121.78, 123.01, 127.21,128.43, 128.46, 129.37, 131.97, 132.98, 134.08, 135.25, 135.52, 149.20.MASS (EI): m/z 357. |
| 87.1% |
With nitric acid; acetic acid at 100℃; for 1h; Inert atmosphere; |
1.3 Preparation of 4,4'-dibromo-2-nitrobiphenyl (A3)
Under nitrogen protection,In 500ml4, 4 '- dibromobiphenyl (20 g, 64.5 mmol) was added sequentially to the round bottom flask,300ml acetic acid, stirring to 100 ° C, dropping 90ml fuming nitric acid, dropping the process gradually produce a large number of white floc, after the drop continued to react for 1 hour. After completion of the reaction, the reaction solution was allowed to cool to room temperature and then poured into an appropriate amount of water to wash out a large amount of bright yellow solid, filtered and the residue was washed several times with water to give 20 l of a pale yellow solid (yield: 87.1% ). |
| 87.6% |
With nitric acid; acetic acid at 100℃; for 6h; |
6.3.5 4,4′-Dibromo-2-nitro-1,1′-biphenyl (10)
To a solution of compound 9 (24g, 76.9mmol) in acetic acid (360mL) was added HNO3 (112.78mL, 2.70mol) dropwisely. The resulting mixture was stirred at 100°C for 6h. The reaction mixture was then extracted with dichloromethane (50mL×3) and the organic layer was dried over MgSO4(S). After filtration and removal of the solvent, the crude product was purified by column chromatography on silica gel using dichloromethane-hexane (1:10) as the eluent to give the final purified product as yellow powder with yield of 87.6% (24.13g). 1H NMR (300MHz, CDCl3) δ: 8.02-8.01 (d, J=2.1Hz, 1H, H6), 7.76-7.73 (dd, J1=8.4Hz, J2=2.1Hz, 1H, H2), 7.56-7.53 (d, J=8.7Hz, 2H, H9, H11), 7.29-7.26 (d, J=8.1Hz, 1H, H3), 7.16-7.13 (d, J=8.4Hz, 2H, H8, H12); 13C NMR (75MHz, CDCl3) δ: 149.20 (C5), 135.52 (C2), 135.25 (C4), 134.07 (C7), 132.98 (C3), 131.97 (C8, C12), 129.37 (C9, C11), 127.21 (C6), 123.02 (C10), 121.79 (C1); HRMS-EI (m/z): [M]+ calcd for C12H7Br2NO2, 354.8844; found 354.8850 [(79Br) (79Br)M]+, 356.8821 [(79Br) (81Br)M]+, 358.8803 [(81Br) (81Br)M]+. |
| 84% |
With nitric acid; acetic acid at 110℃; |
|
| 83% |
With nitric acid; acetic anhydride; acetic acid In dichloromethane for 18h; |
|
| 83% |
With nitric acid; acetic acid |
|
| 81% |
With nitric acid; acetic acid In water at 100℃; |
|
| 78% |
With nitric acid; acetic acid at 100℃; for 2h; |
|
| 77% |
With nitric acid; acetic acid at 110℃; for 6h; |
6 Preparation of 4,4'-dibromo-2-nitrobiphenyl [0165] (compound f-1)
Acetic acid 2-neck RBF put (glacial acetic acid) 300mL 4,4'- dibromo-biphenyl was placed 20g NHO3 70% solution are added to 132mL. And the mixture was stirred for 6 hours the solution at 110 . The yellow transparent liquid is changed to brown. After the reaction it was over gave after cooling to room temperature and the solid washed with water and the precipitated yellow filter. The resulting solid was recrystallized in order to increase the purity of ethanol obtained by 4,4'-dibromo-2-nitrobiphenyl (compound f-1)The (yield: 77%). |
| 65.5% |
With nitric acid; acetic acid at 100℃; Sealed tube; |
3.1 1) Preparation of 4,4'-dibromo-2-nitrobiphenyl (11)
4,4'-dibromobiphenyl (20.0 g, 64.1 mmol) was dissolved in 200 mL of acetic acid and 100 mL of fuming nitric acid (31 mL) diluted with acetic acid was added dropwise to the reaction solution. The reaction flask was sealed at the end of the dropwise addition and the reaction was refluxed at 100 ° C for 1 to 2 hours. The reaction was stopped and cooled to room temperature. The reaction mixture was poured into ice water and stirred under suction to give a pale yellow solid. The residue was washed with water, saturated aqueous sodium bisulfite, water and cold ethanol respectively, and the residue was dried to give Light yellow powdery solid (15 g, 65.5%). |
| 63% |
With nitric acid; acetic acid at 85℃; for 2h; Darkness; Cooling with ice; |
1 Example 1
Dissolve 4,4’-dibromobiphenyl (15.6g, 50mmol) in 150mL acetic acid,Stir in the dark under an ice bath, take 30ml fuming nitric acid and dilute with 50ml acetic acid and add it to the constant pressure dropping funnel.Slowly add dropwise to the reaction solution under dark conditions, slowly increase the reaction temperature to 85°C and reflux for 2h after the addition is complete. Observe the change of the reaction liquid, stop the reaction when the reaction liquid turns from turbidity to transparent, and cool to room temperature naturally.The reaction liquid was slowly poured into ice water to quench, the mixed liquid was suction filtered, and the filter residue was waterWash with saturated sodium bisulfite aqueous solution, water, ice ethanol,The filter residue was then dried to obtain 4,4'-dibromo-2-nitrobiphenyl (12.7g, yield 63%), |
| 60% |
With nitric acid; acetic acid at 0 - 100℃; for 1h; Darkness; |
6.1 1) Synthesis of 4,4-dibromo-2-nitrobiphenyl (27):
4,4'-dibromobiphenyl (20 g, 64 mmol) was added to dissolve200mL acetic acid, ice bath (0 ~ 5 ° C), avoiding light,Take 30mL of fuming nitric acid and dilute with 70mL of acetic acid to add to the constant pressure dropping funnel, slowly add dropwise to the reaction solution in the dark,After the completion of the dropwise addition, the reaction temperature was slowly raised to 100 ° C and refluxed for 1 hour.Observe the change of the reaction solution, and stop the reaction when the reaction solution becomes cloudy and becomes transparent.Cool naturally to room temperature. The reaction solution was slowly poured into ice water and quenched, and the mixture was suction filtered, and the residue was respectively washed with water, saturated aqueous sodium hydrogensulfite solution, water,After washing with ice-cold, the residue was dried to give a pale yellow solid (13.7 g, 60%). |
|
With nitric acid |
|
|
With nitric acid In acetic acid |
|
|
With water; nitric acid; acetic acid for 0.5h; Inert atmosphere; Reflux; |
|
|
With nitric acid; acetic acid at 110℃; for 0.5h; |
|
|
With sulfuric acid; nitric acid |
|
|
With nitric acid; acetic acid at 110℃; |
|
|
With nitric acid; acetic acid In water |
|
|
With nitric acid |
|
|
With nitric acid; acetic anhydride; acetic acid In dichloromethane at 20℃; |
|
|
With nitric acid; acetic acid at 100℃; for 6h; |
|
|
With nitric acid In acetic acid at 100℃; for 1h; |
|
|
With nitric acid; acetic acid at 100℃; |
|
|
With nitric acid; acetic acid |
2
2.5 g (8 mmol) 4,4’-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80%) of 4,4’-dibromo carbazole. The 4,4’-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction. |
|
With nitric acid; acetic acid at 110℃; |
|
|
With nitric acid; acetic acid at 100℃; |
|
|
With sulfuric acid; nitric acid In acetic acid at 110℃; for 1h; |
Syntheses of monomers and polymers
4,4'-Dibromo-2-nitrobiphenyl (7): In a 500 mL flask, 4,4'-Dibromobiphenyl (10 g, 32 mmol) was mixed with acetic acid (200 mL). A mixture of sulphuric acid and nitric acid (respectively 16 mL and 8 mL) was then added dropwise. The reaction mixture was heated at 110 °C for 1 h, allowed to cool down at room temperature, poured into 300 mL of water and filtered. The yellow solid was purified by recrystallization in methanol to obtain a pale yellow solid which was used in the next step without further purification. |
|
With nitric acid; acetic acid for 0.5h; Reflux; |
|
|
With nitric acid; acetic acid at 110℃; |
|
| 30.3 g |
With sulfuric acid; nitric acid In dichloromethane at 10 - 15℃; for 2h; |
1.1; 2.1; 3.1; 4.1; 5.1; 6.1
31.2 g of 4,4'-dibromobiphenyl was dissolved in 312 ml of dichloromethane.The temperature of the control system is between 10-15 °C.A mixed solution of 11.0 g of concentrated nitric acid (65%) and 10.5 g of concentrated sulfuric acid (98%) was slowly added dropwise.After the addition is completed, the heat is reacted at 10-15 ° C for 2 h, and the reaction solution is washed with water, dried,Concentration and ethanol recrystallization gave 30.3 g of 2-nitro-4,4'-dibromobiphenyl. |
|
With nitric acid; acetic anhydride; acetic acid In dichloromethane |
|
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
