2,7-Dibromofluorene

white to off-white crystalline powder

To a solution of fluorene (1.5 g, 9.0 mmol) in CClTo a 250 cm3 round-bottom flask, wrapped in aluminumfoil, was added 10.00 g fluorene (60 mmol) and 50 cm3CHCl3. The solution was cooled to 0 C and 0.14 g ferricchloride (0.9 mmol) was added. Bromine (6.52 cm3, 126 mmol) was added slowly over 15 min at which pointthe ice bath was removed and the solution allowed to warmslowly over 3 h. The mixture was washed with Na2SO3(aq) and extracted with CHCl3 followed by drying withMgSO4, and the solvent was evaporated in vacuum toafford the desired product (19 g, 97 percent yield) as whitepowder without further purification. m.p.: 162–164 C(Ref. [40] 161–164 C).In a 250 mL round bottom flask, Will be 5 g(30.1 mmol)Fluorene solutionTo 50 mL of dry chloroform, 13.25 g 83 mmol (2.75 times) of liquid bromine was dissolved in 30 mL of dry chloroform solution, The above mixed solution was added dropwise to the reaction flask at 0 ° C in a constant pressure dropping funnel and stirred overnight in the dark, and the saturated Na2S2O3 solution was added to the reaction solution to neutralize the excess liquid bromine, Quenching reaction, Dispensing, After the organic layer was washed several times with water, In the organic phase by adding anhydrous MgSO4 dry for half an hour, Filtered to remove anhydrous magnesium sulfate, Vacuum spin to remove the solvent, Recrystallization from ethanol, Afforded the white solid 2, 7-dibromo-9H-fluorene 2a in yieldIn 250 mL round-bottomed flask, 5 g fluorene dissolved in 50 mL dry chloroform, to 4.18 mL (2.74 times) of liquid bromine was dissolved in 30 mL chloroform solution was dried, pressure-equalizing dropping funnel at 0 ° C and was added dropwise to the above mixed reaction flask.Was stirred overnight protected from light, saturated NaIn a 250 mL round bottom flask, Dissolve 5 g of fluorene in 50 mL of dry chloroform, 4.18 mL (2.74 times) of liquid bromine was dissolved in 30 mL of dry chloroform solution, The above mixture was added dropwise to the reaction flask at 0 ° C in a constant pressure dropping funnel.Under dark conditions, stirring overnight, Saturated Na2S2O3 solution was added to the reaction solution and excess liquid bromine, Quench the reaction, liquid separation, After washing the organic layer several times with water, Add anhydrous MgSO4 to the organic phase for half an hour, Filtered to remove anhydrous magnesium sulfate, The solvent was removed by rotary evaporation in vacuo, Recrystallization in ethanol, A white solid 2a was obtained, Yield 95percent.To a solution of fluorene (14.7g, 88.44mmol) in dry chloroform (150mL) at 0°C was added with a solution of BrFluorene (8.31 g, 50.0 mmol, 1.00 eq) was dissolved in chloroform (83 mL, 0.6 M) and iron powder (279 mg, 5.00 mmol, 0.10 eq) was added. The solution was cooled in a water/ice bath to 0 °C. Bromine (5.38 mL, 105.0 mmol, 2.10 eq) in chloroform (42 mL) was added through a dropping funnel over one hour in the dark to the vigorously stirred mixture. After complete addition the mixture was stirred for an additional three hours at 0 °C. Saturated NaAfter inserting the round flask 9H- fluorene (10g, 60.11mmol) in, placed methylene chloride (MC) in 200mL solvent. From 0 slowly injected bromine (6.78mL, 2.2eq). Gave the HBr gas was discharged out of the room temperature Thereafter, the mixture was stirred for 6 hours. After completion of the reaction with aqueous NaOH solution, and extracted with MC and the organic layer with brine to remove the remaining water over anhydrous magnesium sulfate and, after evaporation of the solvent was recrystallized from methanol and the MC 2, 7-dibromo-9Hfluorene of a white solid ( to give a compound e-1) (yield: 88percent).In a 250 ml three-mouth bottle, by adding fluorene (16.6g, 0 . 1mol), iron powder (88 mg, 1 . 57mmol), chcl 100 ml. Ice water bath cooling, instillment bromine (35.2g, 0 . 22mol)/ chcl mixed solution 35 ml. When the temperature is not exceeded in the bottle drops 5 °C. After dropping, so that automatic temperature rise, then reaction under the room temperature condition for 6 hours, saturated sodium bisulfite solution to washing to salmoneous dematerialised. The separated white solid, filtered, and the filtrate combined organic phase, water washing 2 times, remove the sub-layer of iron powder and residue, organic layer with anhydrous MgSOIn a 250 mL three-necked flask, fluorene (24.5 g, 0.1 mol) was added, Iron powder (88mg, 1.57mmol)And methyl chloride 100mL; ice bath cooling, (17.6g, 0.1mol) / chloroform mixed solution 35mL, drop the bottle when the temperature does not exceed 5 ; reaction is completed, filtration, chloroform recrystallization, white solid 20.3g, yield 83percent.In a 250 mL three-necked flask, fluorene (24.5 g, 0.1 mol) was added, Iron powder (88 mg, 1.57 mmol) and chloroform (100 mL)Ice water bath cooling, (17.6 g, 0.1 mol) in chloroform (35 mL) was added dropwise, and the temperature in the bottle was not more than 5 ° C.The reaction was completed, filtered and recrystallized from chloroform to give 20.3 g of a white solid, Yield 83percent.1HNMR, 13CNMR, MS and elemental analysis showed that the resulting compound was the target product.In a 250 mL three-necked flask, a solution of fluorene (24.5 g, 0.1 mol), iron powder (88 mg, 1.57 mmol) and methyl chloride 100 mL; Ice water bath cooling, a solution of 35 mL of a mixed solution of bromine (17.6 g, 0.1 mol) / trichloromethane was added dropwise, Drop the bottle when the temperature does not exceed 5 ; The reaction was completed, filtered and recrystallized from chloroform to give 20.3 g of a white solid in 83percent yield.Fluorene (16.6 g, 0.1 mol) and iron powder (88 mg, 1.57 mmol) were dissolved in 100 mL of chloroform. In an ice bath, 35 mL of chloroform-diluted liquid bromine (35.2 g, 0.22 mol) was slowly added dropwise. When the bottle temperature does not exceed 5 . The reaction was completed, filtered and recrystallized from chloroform to give a beige solid powder (26.9 g, 83percent).In a 250mL three-vial bottle, Add hydrazine (24.5g, 0.1mol), iron powder (88mg, 1.57mmol) and chloroform (100mL);Ice water bath cooling, Bromine (17.6g, 0.1mol) / chloroform mixed solution was added dropwise 35mL, when the bottle temperature does not exceed 5 °C;After the reaction was completed, filtration and recrystallization from chloroform gave 20.3 g of a white solid with a yield of 83percent.BrIn the 1000mL three bottles, A solution of fluorene (60 g, 301 mmol)Iron powder (0.84 g, 15 mmol) and chloroform (400 mL)Ice bath to 5 ° C, Under dark conditions, A solution of liquid bromine (35 mL, 753 mmol) and 115 mL of chloroform was slowly added dropwise to the reaction solution, Drop finished, And stirred at room temperature (stirring speed: 800 rpm) for 12 hours.The reaction was quenched by adding 200 mL of saturated aqueous sodium bisulfite solution to the reaction flask.The reaction mixture was subjected to suction filtration, The residue was washed with saturated aqueous sodium bisulfite solution, Water and ethanol washed three times, After drying the residue, Recrystallization from CHC13 for purification, To obtain 77.8 g of white crystals, Yield: 80percent.In a 1000 mL three-necked flask, A solution of fluorene (60 g, 301 mmol)Iron powder (0.84 g, 15 mmol) and chloroform (400 mL)Ice bath (5 ) in the dark, A solution of bromine (35 mL, 753 mmol)And 115 mL of chloroform were slowly added dropwise to the reaction solution, Plus, The reaction was vigorously stirred at room temperature for 12 hours.A reaction solution was prepared by adding 200 mL of a saturated aqueous solution of sodium bisulfite to the reaction flask.The reaction mixture was suction-filtered, and the residue was washed three times with saturated aqueous sodium bisulfite solution, water and ethanol, dried by filtration and recrystallized from CHCl3 to obtain 77.8 g of white crystals and 80percent yield.The raw material fluorene (5.000 g, 30.0 mmol) was dissolved in 30 ml in a three-neck bottle.Trichloromethane, the three bottles are placed in an ice water bath and cooled to below 0 C.Pipette bromine (3.6 ml, 70.0 mmol) in 5 mlThe chloroform was placed in a constant pressure funnel, and liquid bromine was slowly added dropwise with stirring.After 30 minutes, the addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 4 h.A white solid precipitated. Stop the reaction after 24 h, The mixture was filtered under reduced pressure to give a white solid.The white crystal 2, 7-dibromoindole (W) was obtained.Yield: 7.210 g (79percent).Small molecule derivative (Compound 5) Synthesis of fluorene (see Figure 1):Fluorene 50mL round bottom flask was added the 2 g, 20 mL of chloroform, iron 10.6mg, iceBath cooled to below 0 , and liquid bromine was slowly added dropwise 4.12g 10mL chloroform mixture, a solutionAfter reacted for 2 hours. Aqueous sodium bisulfite to remove excess bromine. MinuteThe chloroform layer was isolated, concentrated, and the solid was filtered, purified by recrystallization with chloroform to give white crystalsBody 2, 7-dibromo fluorene (compound 1) 2.95g, Yield: 78.5percent.Dissolve fluorene (5.00 g, 30.08 mmol) in 40 mL of chloroform solution.A solution of Br2 (3.08 mL) dissolved in 15 mL of chloroform was added dropwise to the above solution and stirred at 0°C for 10 hours in the dark.Stop the reaction and pour the mixed solution into aqueous Na2S2O3 solution.Extract with dichloromethane (15 mL × 3), combine the organic layers with deionized water (25 mL × 3) and saturated brine (20 mL), dry the organic layer over anhydrous magnesium sulfate, and remove the solvent using a rotary evaporator.The crude product is recrystallized from absolute ethanol solution.A white solid of 2, 7-dibromo-fluorene (7.04 g, 72.2percent) was obtained;2, 7-Dibromo-fluorene (6.40 g, 19.75 mmol) and tetrabutylammonium bromide (0.10 g, 0.31 mmol) obtained from the previous reactionDissolve 1-bromododecane (10 mL, 41.65 mmol) in 60 mL of toluene and 25 mL of 50 wtpercent NaOH aqueous solution, and argon at 80 °C for 24 hours under reflux.Stop the reaction and extract the solution with ethyl acetate (25mL x 3). Combine the organic layers with deionized water (25mL x 3)After washing with saturated brine (30 mL), the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed using a rotary evaporator.The crude product was separated by a chromatography column (petroleum ether:dichloromethane=4:1) to give didodecyl-fluoreneas a pale yellow solid (11.30 g, 86.6percent). );Finally, the resulting 2, 7-dibromo-9, 9-didodecyl-fluorene (2.00 g, 3.03 mmol) was reacted in the previous step.Dissolve in 60 mL of dichloromethane, add 10 mL of concentrated sulfuric acid, and cool to 0 °C.Ammonium cerium nitrate (4.98 g, 9.08 mmol) was added in portions to the above mixed solution and the reaction was stirred for 1 hour.Stop the reaction by adding 50 mL of deionized water and extract with dichloromethane (15 mL x 3).The organic phase was washed with deionized water (25 mL×3) and saturated brine (20 mL), respectively.Dry the organic layer by adding anhydrous magnesium sulfate, The solvent was removed using a rotary evaporator and the crude product was separated on a chromatography column (petroleum ether: dichloromethane = 4:1).The orange-yellow product 2, 7-dibromo-9, 9-didoceyl-1, 6-dinitrofluorene (1.7 g, 74.56percent) was obtained.(1) Synthesis of Intermediate 1 (2, 7-dibromofluorene)

Used as a template for N-carbazole-sealed oligomers, which are potential materials for hole transport in OLEDs.

Molecular Weight:324.01
XLogP3:5.1
Exact Mass:323.89723
Monoisotopic Mass:321.89928
Heavy Atom Count:15
Complexity:217
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes