2-Bromo-9,9-dimethylfluorene

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1) take a volume of 100ML two one flask, One flask through the flask was added 5g9, 9-dimethylfluorene, 0.35 g of benzyltriethylammonium bromide, 0.77 g sodium bromate; Sub (2)-I-5 (6.8 g, 35 mmol) was dissolved in Methylene chloride(123 mL), NBS (N-bromosuccimide) (6.85 g, 38.5After the addition mmol) slowly, and the mixture was stirred at room temperature for 24 hours. After the reaction was terminated after addition of 5percent HCl the concentration of impregnated waterIt was added to remove the remaining NBS. That after the extraction with ether and water produced and the organic layer was dried over MgSO4, and concentrate the organicWater silicagel column and the product was recrystallized from 7.46 g: (yield: 78percent).Under the atmosphere of argon, 28 g of 35percent potassium hydride (available from HIROSHIMA WAKO Co., Ltd.) was added to 300 milliliter of anhydrous THF, and then 16 g of fluorenone was added. Thereafter, 20 g of iodomethane (available from HIROSHIMA WAKO Co., Ltd.) was added, and the reaction was allowed to proceed at the refluxing temperature for 72 hours. To the obtained reaction mixture, water was added, and then dilute hydrochloric acid was added. The resultant mixture was treated by extraction with chloroform, and the obtained extract was dried with anhydrous magnesium sulfate. The solvent was removed under a reduced pressure, and the formed solid substance was separated by filtration and washed with methanol. The solid substance obtained above in an amount of 5 g was suspended into 300 milliliter of purified water, and 0.1 g of ferric chloride monohydrate (available from HIROSHIMA WAKO Co., Ltd.) was added to the resultant suspension. Then, an aqueous solution obtained from 1 milliliter of bromine and 100 milliliter of purified water was added dropwise at the room temperature over 1 hour, and the reaction was allowed to proceed at the room temperature for 12 hours. After the formed crystals were separated by filtration, washed with water and methanol and dissolved into 200 milliliter of chloroform, the resultant solution was washed with an aqueous solution of sodium hydrogencarbonate and water and dried with anhydrous magnesium sulfate, and the solvent was removed by distillation. After 100 milliliter of hexane was added to the resultant mixture, the formed crystals were separated by filtration, and 5.4 g of the crystals were obtained. Since m/z=277 and 275 in FD-MS of the obtained compound, which corresponded to C15H16Br=276, the compound was identified to be 9, 9'-dimethyl-2-bromofluorene (the yield: 20percent).[Embodiment 13]; [0467]In this embodiment, a synthetic method of9, 10-bis(9, 9-dimethylfluorene-2-yl)-2-[iV-phenyl-iV-(9-phenyl-9H-carbazol-3-yl)amino] anthracene (abbreviation: 2PCADFA), which is the anthracene derivative of the present invention represented by Structural Formula (207), is specifically described. [0468](207)[0469][Step 1] Synthesis of 2-bromo-9, 9-dimethylfluorene[0470](i) Synthesis of 2-bromo-9, 9-dimethylfluorene.A synthetic scheme of 2-bromo-9, 9-dimethylfluorene is shown in (C-27). [0471][0472] Step 1: Synthesis of 2-bromo-9, 9-dimethylfluoren] [0340]A synthetic scheme of 2-bromo-9, 9-dimethylfluoren in Step 1 is shown in the following (F-I). [0341][0342]In a 500-mL conical flask, 12.5 g (51 mmol) of 2-bromofluorene, 8.5 g (51 mmol) of potassium iodide, 14.3 g (0.50 mol) of potassium hydroxide, and 250 mL of dimethyl sulfoxide were stirred for 30 minutes. Then, 10 mL of methyl iodide was added to this mixture little by little. This mixture was stirred at room temperature for 48 hours. After the reaction, 400 mL of chloroform was added to the reaction solution and this mixture was stirred. This solution was washed with IN hydrochloric acid, a saturated sodium carbonate solution, and a saturated saline solution in this order. Magnesium sulfate was added to the obtained organic layer to remove moisture. [0343]This mixture was subjected to suction filtration and concentrated. Then, a 2-bromofluorene (25 g, 102.0 mmol), iodomethane (43.4 g, 306.0 mmol) and DMSO (300 mL) were placed in a 1000 mL three-necked round flask and dissolved by stirring in a nitrogen atmosphere. Potassium-tert-butoxide (32.1 g, 285.6 mmol) was dissolved in 400 mL of DMSO and slowly added dropwise. The mixture was stirred at room temperature for 12 hours, then stirred at 80 ° C for 1 hour, and then cooled to room temperature. Mixed with 1000 mL of water and extracted with normal hexane. The organic mixture was washed three times with distilled water, and the water was removed with anhydrous magnesium sulfate (MgSO 4). The solvent was removed by a rotary evaporator, and the residue was purified by using n-hexane using a silica gel chromatograph tube and recrystallized from n-hexane to obtain a white solid 2-Bromo-9, 9'-dimethylfluorene 27.0 g (yield: 96.9percent) was obtained.These compounds were obtained following an essentially similar procedure. An illustrative example is provided for 8: 2-bromofluorene (4.90 g, 0.02 mol) was dissolved in anhydrous THF (100 mL) in a three-necked round-bottom flask fitted with a magnetic stirrer, a condenser and a N2-bromofluorene (89.0 g, 0.363 mol) was dissolved in 1.3 liter of THF and after cooling to 5°C, potassium tert-butoxide (102 g, 0.908 mol) was added, methyl iodide (565 ml, 0.908 mol) was added dropwise at 5°C and after the dropwise addition, the resulting solution was stirred at room temperature for 5 hours to obtain 2-bromo-9, 9-dimethylfluorene in a yield 87percent.2-bromofluorene (20 g, 82 mmol), potassium iodide (13.54 g, 82 mmol) and potassium hydroxide (22.89, 408 mmol) were placed in a 1000 ml round bottom flask together with 400 ml of dimethyl sulfoxide, After stirring, iodomethane (34.75 g, 245 mmol) was added dropwise for 1 hour and reacted at room temperature for 24 hours.After the completion of the reaction, the reaction solution was poured into 600 ml of chloroform, stirred for 20 minutes, and extracted with 1 L of 1N hydrochloric acid. The organic layer was collected and washed twice with 1 L of brine, and then the organic layer was concentrated. 19.5 g (yield: 87.5percent) was obtained.

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

Molecular Weight:273.17
XLogP3:5.1
Exact Mass:272.02006
Monoisotopic Mass:272.02006
Heavy Atom Count:16
Complexity:271
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes