2,7-Dibromo-9,9'-spiro-bifluorene

white powder

2) Synthesis of a compound 2 After the compound 1 (14.28 mmol, 7 g) was dissolved in 70 ml of acetic acid, three drops of concentrated HCl were added thereto, and refluxing was conducted for 12 hours. After the reaction, the resulting mixture was slowly dropped into 250 ml of water to produce a precipitate. After the precipitate was dried, purification was conducted using a developer having hexane and ethyl acetate in a volume ratio of 10:1 to produce a compound 2 (12.72 mmol, 6 g) (Yield 89 percent).Under the protection of argon, add 2, 7-dibromofluorenone 10 mmol to the reaction flask.11mmol of 2-fluorobiphenyl and 20ml of tetrahydrofuran solvent, after stirring evenly, 22 mmol of lithium metal tablets were added to the reaction solution in batches.Then, the temperature is raised to about 40 ° C, and the reaction is carried out for 24 hours.After the reaction was completed and returned to room temperature, the reaction was quenched with 20 mL of 1N aqueous hydrochloric acid.The organic phase was separated, and the tetrahydrofuran was evaporated to dryness on a rotary evaporator.The crude solid was added to 10 ml of acetic acid.Heating to 120 ° C for 24 hours, after the end of the ring closure reactionFiltration gave crude 2, 7-dibromo-9, 9'-spirobifluorene.The crude product uses a mixed solvent of dichloromethane and n-hexane as an eluent.Perform column chromatography separation, and the chromatographic silica gel is 200-300 mesh.Finally, the product 2, 7-dibromo-9, 9'-spirobifluorene 4.08g was obtained.The yield was 86percent.2-iodobiphenyl 1mol was dissolved in THF after the dropwise addition of n-BuLi at -78 a stirred for 1 hour After dropwise dissolving 2, 7-dibromo-9H-fluoren-9-one 1mol in THF. The temperature was raised to room temperature and then stirred for one hour to confirm the completion of the reaction and extracted with CH2Cl2 and 1N HCl. The organic layer was dried over MgSO4 to give the Intermediate K was purified by column chromatography and recrystallized (yield 71percent). After the K intermediate was dissolved in acetic acid to complete the addition of concentrated hydrochloric acid for 1 hour under reflux 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 and purified by column chromatography and recrystallization to give the intermediate L (Yield 82percent).To 180 g of a toluene solution of 9- (2-biphenyl) -2, 7-dibromo-9-fluorene alcohol obtained in Example 3, Concentrated sulfuric acid 18.0 g (0.180 mol, 2.00 M.R.) was charged, The reaction was carried out at room temperature for 2 hours.After caustic water was added to the obtained reaction mixture solution to neutralize it, Toluene was added to crystallize, By filtration and drying, 35.9 g of 2, 7-dibromo-9, 9'-spirobifluorene as white crystals(Yield: 80percent, total yield from 72percent, purity: 95percent).22 g (45.0 mmol) of 9-biphenyl-2-yl-2, 7-dibromo-9-fluorenol, and 100 mL of glacial acetic acid were placed in a 300 mL three-necked flask, several drops of concentrated hydrochloric acid were added, and the mixture was refluxed. After the reaction, the precipitates were filtered The precipitate was recrystallized with ethanol, and 12.3 g of 2, 7-dibromo-spiro-9, 9'-bifluorene was obtained as a white solid, in a yield of 57percent. [0359]A synthesis scheme (h-4) of 2, 7-dibromo-9, 9'-spiro-bifluorene is shown below. [0360]A solution of 10 mL of o-dibromobenzene (0.1 mmol) in methyl tetrahydrofuran was added dropwise to a solution of 5 mL of phenylmagnesium bromide (0.11 mmol) in methyltetrahydrofuran under argon atmosphere at 80 ° C. Reaction 12 h. The reaction solution was then added dropwise to 10 mL of 2, 7-dibromofluorenone (0.1 mmol) in ether. The mixture was heated to reflux for 2 h, hydrolyzed and filtered. The solid was dissolved in 5 mL of mixed acid (glacial acetic acid and hydrochloric acid) (200-300 mesh silica gel) to give the product 2, 7-dibromo-9, 9 '-spirobifluorene , which was purified by column chromatography on silica gel eluted with a mixed solvent of methylene chloride and n-hexane.36 . 2 mg, yield 76.2percent. The resulting 2, 7-dibromo-9, 9-spirobifluorene was reacted with lithium diphenylphosphine (0.15 mmol) in tetrahydrofuran solvent. After refluxing for 12 h, methanol was added to the reaction solution, (200-300 mesh silica gel) to obtain the desired product. 2-Bis (diphenylphosphino) -9, 9-spirobifluorene 35. 9 mg was obtained by the same procedure as that of Example 1, Mg, and the yield was 70.1percent.c l) 2) Synthesis of a compound 2 After the compound 1 (14.28 mmol, 7 g) was dissolved in 70 ml of acetic acid, three drops of concentrated HCl were added thereto, and refluxing was conducted for 12 hours. After the reaction, the resulting mixture was slowly dropped into 250 ml of water to produce a precipitate. After the precipitate was dried, purification was conducted using a developer having hexane and ethyl acetate in a volume ratio of 10:1 to produce a compound 2 (12.72 mmol, 6 g) (Yield 89 percent).Under the protection of argon, add 2, 7-dibromofluorenone 10 mmol to the reaction flask.11mmol of 2-fluorobiphenyl and 20ml of tetrahydrofuran solvent, after stirring evenly, 22 mmol of lithium metal tablets were added to the reaction solution in batches.Then, the temperature is raised to about 40 ° C, and the reaction is carried out for 24 hours.After the reaction was completed and returned to room temperature, the reaction was quenched with 20 mL of 1N aqueous hydrochloric acid.The organic phase was separated, and the tetrahydrofuran was evaporated to dryness on a rotary evaporator.The crude solid was added to 10 ml of acetic acid.Heating to 120 ° C for 24 hours, after the end of the ring closure reactionFiltration gave crude 2, 7-dibromo-9, 9'-spirobifluorene.The crude product uses a mixed solvent of dichloromethane and n-hexane as an eluent.Perform column chromatography separation, and the chromatographic silica gel is 200-300 mesh.Finally, the product 2, 7-dibromo-9, 9'-spirobifluorene 4.08g was obtained.The yield was 86percent.2-iodobiphenyl 1mol was dissolved in THF after the dropwise addition of n-BuLi at -78 a stirred for 1 hour After dropwise dissolving 2, 7-dibromo-9H-fluoren-9-one 1mol in THF. The temperature was raised to room temperature and then stirred for one hour to confirm the completion of the reaction and extracted with CH2Cl2 and 1N HCl. The organic layer was dried over MgSO4 to give the Intermediate K was purified by column chromatography and recrystallized (yield 71percent). After the K intermediate was dissolved in acetic acid to complete the addition of concentrated hydrochloric acid for 1 hour under reflux 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 and purified by column chromatography and recrystallization to give the intermediate L (Yield 82percent).To 180 g of a toluene solution of 9- (2-biphenyl) -2, 7-dibromo-9-fluorene alcohol obtained in Example 3, Concentrated sulfuric acid 18.0 g (0.180 mol, 2.00 M.R.) was charged, The reaction was carried out at room temperature for 2 hours.After caustic water was added to the obtained reaction mixture solution to neutralize it, Toluene was added to crystallize, By filtration and drying, 35.9 g of 2, 7-dibromo-9, 9'-spirobifluorene as white crystals(Yield: 80percent, total yield from 72percent, purity: 95percent).22 g (45.0 mmol) of 9-biphenyl-2-yl-2, 7-dibromo-9-fluorenol, and 100 mL of glacial acetic acid were placed in a 300 mL three-necked flask, several drops of concentrated hydrochloric acid were added, and the mixture was refluxed. After the reaction, the precipitates were filtered The precipitate was recrystallized with ethanol, and 12.3 g of 2, 7-dibromo-spiro-9, 9'-bifluorene was obtained as a white solid, in a yield of 57percent. [0359]A synthesis scheme (h-4) of 2, 7-dibromo-9, 9'-spiro-bifluorene is shown below. [0360]Diethyl ether (10 mL) was added to magnesium (1.9 g, 25.6 mmol), and 2-bromobiphenyl (5 g, 21.6 mmol) diluted in diethyl ether (20 mL) was slowly added dropwise, and the mixture was stirred under reflux for 3 hours. In diethyl ether (40 mL), dissolved was 2, 7-dibromofluorenone (6.7 g, 20 mmol), and the solution was added to the mixture previously prepared. The resultant mixture was stirred under reflux for 12 hours, and cooled to ambient temperature. The precipitate produced was filtered under reduced pressure, and dissolved in acetic acid (40 mL). While heating the solution under reflux, concentrated hydrochloric acid was slowly added dropwise thereto. After four hours, the reaction was completed to give Compound (126) (5.2 g, 10.9 mmol).

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

Molecular Weight:474.2
XLogP3:7.8
Exact Mass:473.94418
Monoisotopic Mass:471.94623
Heavy Atom Count:27
Complexity:523
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes