2-Bromo-9,9′-spirobi[9H-fluorene]

Off-white to light yellow crystal or powder2-Bromo-9, 9’-spirobifluorene is a derivative of 9,9'-spirobifluorene. It is a quite useful blue light emitting material used in the organic light emitting diodes (OLEDs). It possesses high photoluminescence efficiency and good chemical stability. Moreover, It has high glass-transition temperature, excellent thermal stability and easy color tenability through introducing low band gap co-monomers.

2-bromo-1, 10-biphenyl (2.16 g, 9.27 mmol, 1.15 equiv) was dissolved in dry THF (40 mL) under argon atmosphere, cooled at -78 °C, and stirred during 10 min at this temperature. A 2.5M n-BuLi solution in THF (4.31 mL, 10.78 mmol, 1.34 equiv) was then slowly injected via a seringue, at -78 °C. The resulting yellow mixture was stirred at the same temperature for 30 min. 2-bromo-9H-fluoren-9-one (2.08 g, 8.03 mmol) in dry THF (35 mL) was then added dropwise, and the mixture was stirred for another 30 min at -78 °C, and allows warming up to room temperature gradually and stirred overnight. Saturated brine solution (10 mL) was added, and the mixture was extracted twice with ethyl acetate (2x30 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Without other purification, the crude was dissolved into a mixture of acetic acid/hydrochloric acid (50 mL/5 mL) and warmed at 70 °C during 2 h under stirring. Then, the mixture was poured into water/ice (200 mL), and the solution was neutralized with solid sodium hydroxide until pH 7. Then the organic layer was extracted three times with dichloromethane (3x50 mL). The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (light petroleum/dichloromethane 95/5) to afford a colourless solid (2.14 g). [column conditions: Silica cartridge 40 g (Serlabo); solid deposit on CelitePreparation of Structural Formula 48B; Structural Formula 48A (27.3 g, 66.1 mmol) was added to 200 ml of glacial acetic acid, and heated, and 0.1 ml of sulfuric acid was added thereto, and heated and agitated for 1 hour. The solid that was generated after the temperature was lowered to normal temperature was filtered, washed with 300 ml of water, and 100 ml of ethanol, and dried to obtain Structural Formula 48B (25.4 g, yield 97percent). MS: [M+H]The intermediate A Was dissolved in acetic acid and the addition of concentrated hydrochloric acid was refluxed for 1 hour to complete the reaction.It was extracted using ether and water and the organic layer was washed with mwot Sat NaHCO3. The organic layer was dried over MgSO4 column chromatography and recrystallization to obtain the intermediate B by (Yield: 85percent).2-iodobiphenyl 2.80g (10mmol) was dissolved in 15ml THF at-78 degree C, 2.5M n-BuLi 4ml was slowly added dropwise at -78 degree C in 30ml THF and then stirred for 1 hour. 2-bromo-9H-fluorene-9-one 2.59 g(10mmol) was added slowly and the temperature was raised to room temperature. After completion of the reaction, 2N HCl was added, and the organic layer was extracted with MC, water in the organic layer was removed, dried over anhydrous MgSO4, and the organic layer was concentrated under reduced pressure by column using Hex: MC = 5: 1 to give intermediate C 3.27g (79percent). Intermediate C was dissolved in acetic acid, concentrated hydrochloric acid was added and refluxed for 1 hour. After completion of the reaction, the organic layer was extracted with ether and water, and washed with Sat NaHCO3. The organic layer was dried over MgSO4, concentrated using Hex: EA = 5:1 by column and recrystallized to obtain 3.20 g intermediate D (81percent).To a refluxing solution OF 2-BROMO-9- (2-BIPHENYL)-9-FLUORENONE (3.0 g, 7. 26 mg) in 50 ML acetic acid was added a few drops of concentrated hydrochloric acid. Refluxing was continued for 30 minutes. The cooled mixture was poured into 200 mL water and the obtained solid filtered, dried and recrystallized from CHLOROFORM/ETHANOL to give 2-bromo-9, 9-spirobifluorene (2.26 g, 79percent yield).A 100 ml three neck distilling flask was charged with magnesium (1.26 g, 0.052 mol) . Vacuum was formed in a system. The magnesium was heated to stir for 30 minutes to be activated. After cooling to room temperature, nitrogen gas stream was formed in the system. Then, 5 ml diethyl ether and a few drops of dibromoethane were added. And then, 2-bromobiphenyl (11.65 g, 0.050 mol) dissolved in 15 ml diethyl ether was slowly dropped. After dropping, the reaction was refluxed for 3 hours to be a Grignard reagent. A 200 ml three neck distilling flask was charged with 2-bromofluorenone (11.7g, 0.045 mol) and 40 ml diethyl ether. The synthesized Grignard reagent was slowly dropped to the reacted solution. After the dropping, the solution was refluxed for 2 hours and stirred at room temperature overnight. After reaction, the reacted solution was washed with saturated ammonium chloride solution twice, and a water layer was extracted with ethyl acetate twice and washed with saturated salt solution twice with an organic layer. After drying with magnesium sulfite, the reacted solution was suctioned and filtrated, and condensed to give 18.76 g 9- (2-biphenylyl)-2-bromo-9-fluorenol in a solid state in a yield of 90percent. A 200 ml three neck distilling flask was charged with the synthesized 9- (2-biphenylyl)-2-bromo-9-fluorenol g, 0.045 mol), 100 ml glacial acetic acid, and a few drops of concentrated hydrochloric acid to be refluxed for 2 hours. After reaction, deposits were collected by saturation and filtration, and filtrated and washed with saturated sodium hydrogencarbonate and water. Obtained brown solid matter was recrystallized from ethanol to give light brown powdery solid matter weighed 10.24 g in a yield of 57percent. The Next, 18.76 g (0.045 mol) of the synthesized 9-(2-biphenylyl)-2-bromo-9-fluorenol and 100 mL of glacial acetic acid were put into a 200-mL three-neck flask. A few drops of concentrated hydrochloric acid were added and the mixture was refluxed for 2 hours. After the reaction, the precipitate was recovered by suction filtration, and washed by filtration with a saturated aqueous sodium hydrogen carbonate solution and water. The obtained brown solid was recrystallized with ethanol, thereby obtaining 10.24 g of a light-brown powder solid with a yield of 57percent. This light-brown powder solid was identified as 2-bromo-spiro-9, 9'-bifluorene by a proton nuclear magnetic resonance method (18.76 g (0.045 mol) of the synthesized 9-(biphenyl-2-yl)-2-bromo-9-fluorenol and 100 mL of glacial acetic acid were put in a 200 mL three-necked flask, several drops of concentrated hydrochloric acid were added, and the mixture was refluxed for 2 hours. After the reaction was complete, a precipitate was collected by suction filtration, and the precipitate was filtered and washed with a saturated sodium hydrogen carbonate solution and water. The brown solid obtained was recrystallized with ethanol, and a light-brown powdered solid was obtained, weighing 10.24 g in a yield of 57percent. It was confirmed that this light-brown powdered solid was 2-bromo-spiro-9, 9'-fluorene by a nuclear magnetic resonance method (NMR). [0273][Step 3] Step 1-2: Synthesis of 2-bromo-spiro-9, 9'-bifluoren][0363]A synthetic scheme of 2-bromo-spiro-9, 9'-bifluoren in Step 1-2 is shown in the following (G-l-2).[0364][0365]In a 200-mL three-neck flask, 18.76 g (0.045 mol) of the synthesized 9-(biphenyl-2-yl)-2-bromo-9-fluorenol and 100 mL of glacial acetic acid were put, 18.76 g (0.045 mol) of synthesized 9- (biphenyl-2-yl) -2-bromo-9-fluorenol and 100 ml of glacial acetic acid were added to a 200 ml three-necked flask, The mixture was refluxed for 2 hours. When the reaction is complete, the precipitate is collected by suction filtration, and the precipitate is filtered and washed with saturated sodium hydrogencarbonate and water. The brown solid obtained was recrystallized from ethanol to give 10.24 g of a slightly brown powder solid in 57percent yield. Using nuclear magnetic resonance (NMR), it was confirmed that the slightly brown powdered solid was 2-bromo-spiro-9, 9'-fluorene.2.4.1 0.1 mmol) solution of methyl tetrahydrofuran was added dropwise to a solution of 5 mL of phenylmagnesium bromide (0.09 mmol) in methyl tetrahydrofuran under argon atmosphere at 50 ° C. The mixture was stirred Reaction 8 h. The reaction solution was then added dropwise to 5 mL of 2-bromofluorenone (0.1 mol) in diethyl ether. After refluxing for 2 h, the product was hydrolyzed and filtered to give a solid in 10 mL of mixed acid (glacial acetic acid and hydrochloric acid) at 75 ° C. (200-300 mesh silica gel), dried to give 2-bromo-9, 9 '-spirobifluorene 30. 9 mg, and then dried over anhydrous magnesium sulfate, dried over anhydrous magnesium sulfate, and filtered to give a solid which was chromatographed on silica gel using a mixture of dichloromethane and n- With a rate of 78.2 per cent. The resulting 2-bromo-9, 9-spirobifluorene was reacted with lithium diphenylphosphine (0. 075 mmol) in 5 mL of tetrahydrofuran and refluxed for 5 h. Methanol was added to give a solid which was washed with water and filtered to give a solid. (200-300 mesh silica gel) to give 31.4 mg of diphenyl-2- (9, 9'-spirobifluorenyl) phosphine in a yield of 80.5percent by column chromatography using hexane-hexane as the eluent.0.1 mmol) solution of methyl tetrahydrofuran was added dropwise to a solution of phenylmagnesium bromide (0.15 mmol) in methyl tetrahydrofuran (5 mL) under argon atmosphere at a reaction temperature of 100 ° C. The reaction was stirred for 20 h. Then the solution was added dropwise to 10 mL of 2-bromofluorenone (0. 1 mmol) in ether. After refluxing for 2 h, the solution was hydrolyzed and filtered. The solid was subjected to reaction at 75 ° C for 4 h in 5 mL of mixed acid (glacial acetic acid and hydrochloric acid). The crude solid was collected by column chromatography (200-300 mesh silica gel) using a mixture of methylene chloride and n- -bromo-9, 9'-spirobifluorene 30.0 mg, yield 76.0percent. The resulting 2-bromo-9, 9-spirobifluorene was reacted with lithium diphenylphosphine (0. 075 mmol) in 10 mL tetrahydrofuran solvent. After refluxing for 5 h, 10 mL of methanol was added to the reaction solution, (200-300 mesh silica gel) to give the desired product diphenyl-2- (9, 9'-spirobifluorenyl) phosphine The resulting product was purified by silica gel column chromatography (eluted with toluene-hexane) 30. 3 mg, yield 81.1percent.

Pharmaceutical intermediates are also important intermediates for the synthesis of optoelectronic materials

Molecular Weight:395.3
XLogP3:7.1
Exact Mass:394.03571
Monoisotopic Mass:394.03571
Heavy Atom Count:26
Complexity:518
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes