2-Bromo-9,9-diphenylfluorene

off-white powder

1) 10 mmol trifluoroacetic acid, 1.5 mmol anhydrous aluminum trichloride and 150 mmol dry benzene in a flaskMix well A liquid;2) 10 mmol of 2-bromo-9-phenyl-fluorene-9-ol and 90 mmol of dry benzene were mixed to give B solution;3) B was added dropwise to Solution A while stirring under argon, 2-bromo-9-phenyl-fluorene-9-ol in Solution BAnd A liquid trifluoroacetic acid molar ratio of 1: 1, mixing process control system temperature does not exceed 45 ;4) the system temperature to 75 , the reaction 1.5 h; and then maintain the system temperature and add 5 mmol trifluoroacetic acid; continueReaction 4h after the end of the reaction.5) separation and purification to be 2-bromo-9, 9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join250 mmol of ice water; stratified, the organic phase was neutralized with saturated sodium bicarbonate to pH, extracted with ethyl acetate, and the extract was concentrated to give a white solid powder product with a yield of 98.6percent.10 mmol of 2-bromo-9-phenyl-fluoren-9-ol and 170 mmol of benzene were mixed, Stirring up to 64 ° C, through the addition of sufficient hydrogen bromide gas, until the TLC monitoring to the basic disappearance of raw materials, ventilation is completed, The reaction system was heated to reflux temperature, refluxed for 2 h, Return the water at the same time using the water separator to separate the system;The system was cooled to 20 ± 2 , in 1h by adding the catalyst in batches, Heated to 45 after 5h reaction;Wherein the catalyst consists of 12 mmol of anhydrous aluminum trichloride and 3 mmol of anhydrous ferric chloride, The catalyst was added in three batches, and the weight ratio was three: 2: 1;Separation and purification to obtain 2-bromo-9, 9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join240 mmo 1 ice water; layered, organic phase neutralized with saturated sodium bicarbonate to pH, ethyl acetate was added and the extract was concentrated to give the product as a white solid, yield 95.1percent.1) 10 mmol trifluoroacetic acid, 1.5 mmol anhydrous aluminum trichloride and 150 mmol dry benzene in a flaskMix well A liquid;2) 10 mmol of 2-bromo-9-phenyl-fluorene-9-ol and 90 mmol of dry benzene were mixed to give B solution;3) B was added dropwise to Solution A while stirring under argon, 2-bromo-9-phenyl-fluorene-9-ol in Solution BAnd A liquid trifluoroacetic acid molar ratio of 1: 1, mixing process control system temperature does not exceed 45 ;4) the system temperature to 75 , the reaction 1.5 h; and then maintain the system temperature and add 5 mmol trifluoroacetic acid; continueReaction 4h after the end of the reaction.5) separation and purification to be 2-bromo-9, 9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join250 mmol of ice water; stratified, the organic phase was neutralized with saturated sodium bicarbonate to pH, extracted with ethyl acetate, and the extract was concentrated to give a white solid powder product with a yield of 98.6%.10 mmol of 2-bromo-9-phenyl-fluoren-9-ol and 170 mmol of benzene were mixed, Stirring up to 64 C, through the addition of sufficient hydrogen bromide gas, until the TLC monitoring to the basic disappearance of raw materials, ventilation is completed, The reaction system was heated to reflux temperature, refluxed for 2 h, Return the water at the same time using the water separator to separate the system;The system was cooled to 20 ± 2 , in 1h by adding the catalyst in batches, Heated to 45 after 5h reaction;Wherein the catalyst consists of 12 mmol of anhydrous aluminum trichloride and 3 mmol of anhydrous ferric chloride, The catalyst was added in three batches, and the weight ratio was three: 2: 1;Separation and purification to obtain 2-bromo-9, 9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join240 mmo 1 ice water; layered, organic phase neutralized with saturated sodium bicarbonate to pH, ethyl acetate was added and the extract was concentrated to give the product as a white solid, yield 95.1%.Diethyl ether (50 mL) was added to magnesium (4.9 g, 200 mmol), and bromobenzene (31.4 g, 200 mmol) diluted in diethyl ether (150 mL) was slowly added dropwise thereto, and the mixture was stirred under reflux for 4 hours. In diethyl ether (40 mL), dissolved was 2-bromofluorenone (25.9 g, 100 mmol), and the solution was added to the Grignard solution previously prepared. The resultant mixture was stirred under reflux for hours. The precipitate produced was filtered to obtain Compound (112) (15 g, 36 mmol), which was then dissolved in benzene (145 mL). While heating the solution, trifluoromethanesulfonic acid (6.6 mL, 72 mmol) was slowly added dropwise. After 30 minutes, the reaction mixture was added to cold saturated aqueous sodium carbonate solution (400 mL). The organic layer was extracted with ethyl acetate (370 mL), and the extract was washed with distilled water (350 mL), dried over magnesium sulfate, and distilled under reduced pressure to obtain Compound (113) (15.3 g, 38.5 mmol).Combine 3-chloro-10H phenoxazine (3g, 13.78mmol), 3-bromodibenzothiophene (5.48g, 13.78mmol), potassium carbonate (4.76g, 34.46mmol), cuprous iodide (0.13g, 0.69mmol) ), O-phenanthroline (0.25g, 1.38mmol) and 18-crown-6 (0.18g, 0.69mmol) were added to N, N-dimethylformamide (30mL), and the system was heated to 150 C under nitrogen protection , Stir for 15 hours; After the reaction solution was cooled to room temperature, extract with ethyl acetate, wash the organic phase with water to neutrality, add magnesium sulfate to the organic phase to dry, filter the filtrate to remove the solvent under reduced pressure; use n-heptane system for the crude product Recrystallization purification was performed to obtain a solid intermediate ID (5.6 g, yield 76%).In a nitrogen environment I-2 (100 g, 299 mmol) was dissolved in 1.2 L of toluene, Here, In a round bottom flask, Add 2.0g of Under nitrogen protection, 4-bromo-4'-adamantyl biphenyl 82.797mmol, 4-aminobiphenyl 82.797mmol, toluene 608mL, sodium tert-butoxide 248.391mmol were added to the reaction flask, stirred, and heated to 70 C Slowly add Pd2dba30.82797mmol and s-PHOS 1.6560mmol. After the addition is complete, continue to warm to 105 C and reflux for 2h, then lower the temperature to 70 C, 81.141 mmol of 2-bromo-9, 9-diphenylhydrazone was heated to 105 C. and refluxed for 6 hours. After the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 25 was dried. Yield: 87%.5.43 g (10 mmol) of Intermediate 7-2, 3.97 g (10 mmol) of

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

Molecular Weight:397.3
XLogP3:7.4
Rotatable Bond Count:2
Exact Mass:396.05136
Monoisotopic Mass:396.05136
Heavy Atom Count:26
Complexity:455
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes