9,9-Dimethyl-2-iodofluorene

2-Iodofluorene (3 g; 10.27 mmol, 1 equiv) was dissolved in 50 mL of anhydrous tetrahydrofuran. Thesolution was cooled to 0°C and 2.6 g of potassium tert-butoxide (23.16 mmol, 3equiv) was added. During the process, the transparent solution became red.After the solution had been stirred for 10 min, 1.44 g of iodomethane(23.16 mmol, 3 equiv) was added, turning the red solution milky. The solution wasreturned to room temperature and stirred for another 12 hours. After 100 mLdeionized water was added, the solution was extracted with ethyl acetate (100mL X 3). The combined organic solution was then dried over magnesium sulfate, and filtered off. The filtrate was condensed under vacuum to obtain a viscousliquid. Further purification by column chromatography (all n-hexane) on silicagel afforded 3.0 g of product 1 in a yield of 91percent. [Step 1] 2-2: Synthesis of 9, 9-dimethyl-2-iodofluorene: Potassium tert-butoxide (21.8 g, 0.19 mol) was added to cooled anhydrous tetrahydrofuran, in which 2-iodofluorene(25.0 g, 85.6 mmol) was dissolved, and then stirred at room temperature for 1.5 hours to prepare a first mixedsolution. Subsequently, methyl iodide (28.2 g, 0.19 mol) was added to the first mixed solution to prepare a second mixedsolution, and then the second mixed solution was stirred for 2 hours to obtain potassium iodide. Subsequently, theobtained potassium iodide was filtered, a solvent was removed under reduced pressure, and a reaction product wasseparated by silica column chromatography (hexane). The yield of the reaction product was 70percent.1H NMR(300 MHz, CDCl3) δ(TMS, ppm): 1.47(6H, s, -CH3), 7.31(2H, m, Ar-H)), 7.45(2H, m, Ar-H), 7.66(1H, d, Ar-H), 7.73(1H, d, Ar-H), 7.85(1H, s, Ar-H)1 g (3.44mmol) of 2-iodofluorene and 100 mL of dimethylsulfoxidewere put into a 500 mL three-neck round-bottom flask.Subsequently, 0.04 g (0.22 mmol) of benzyltrimethylammonium chloride and 1 mL of 50percent sodium hydroxide aqueous solution were added to the mixture. This mixture was stirred at RT for 3 h. Thereafter, 0.76 g (5.2 mmol) of iodomethane was added into the reaction mixture, which was stirred at RT for an additional 3 h. After completion of the reaction, the reaction solution was washed with 1.0 mol/L hydrochloric acid; a water layer was extracted three times with ethyl acetate. The collected organic layer was washed with saturated saline, and then dried with magnesium sulfate.After drying, the mixture was subjected to suction filtration, and the filtrate was concentrated. An obtained residue was purified by silica gel column chromatography (hexane aseluent), and an obtained solution was concentrated. The residue solid was recrystallized with a mixed solvent of chloroform and hexane to yield 0.7 g of a white, powdery solid of 2-iodo-9, 9-dimethylfluorene (64percent yield) (the chemical structure in Scheme 2).1H NMR (CDCl3, 400MHz) δH7.92 (s, 1H), 7.70 (d, J= 8.4 Hz, 1H), 7.66 (d, J =8.4 Hz 1H), 7.60 (d, J= 8.4 Hz, 1H), 7.47 (d, J= 8.4 Hz, 1H), 1.37 (s, 6H), MS (GC-mass): m/z320.0 [M+]; C15H13I(320.1).2-Iodofluorene (3 g; 10.27 mmol, 1 equiv) was dissolved in 50 mL of anhydrous tetrahydrofuran. Thesolution was cooled to 0C and 2.6 g of potassium tert-butoxide (23.16 mmol, 3equiv) was added. During the process, the transparent solution became red.After the solution had been stirred for 10 min, 1.44 g of iodomethane(23.16 mmol, 3 equiv) was added, turning the red solution milky. The solution wasreturned to room temperature and stirred for another 12 hours. After 100 mLdeionized water was added, the solution was extracted with ethyl acetate (100mL X 3). The combined organic solution was then dried over magnesium sulfate, and filtered off. The filtrate was condensed under vacuum to obtain a viscousliquid. Further purification by column chromatography (all n-hexane) on silicagel afforded 3.0 g of product 1 in a yield of 91%. 1H NMR (300 MHz, CDCl3, delta) 1.47(s, 6H), 7.34-7.36(m, 2H), 7.40-7.45(m, 1H) 7.48(s, 1H), 7.64-70(m, 2H), 7.75-7.76(m, 1H)[Step 1] Synthesis of 2-2: Synthesis of 1 g (3.44mmol) of 2-iodofluorene and 100 mL of dimethylsulfoxidewere put into a 500 mL three-neck round-bottom flask.Subsequently, 0.04 g (0.22 mmol) of benzyltrimethylammonium chloride and 1 mL of 50% sodium hydroxide aqueous solution were added to the mixture. This mixture was stirred at RT for 3 h. Thereafter, 0.76 g (5.2 mmol) of iodomethane was added into the reaction mixture, which was stirred at RT for an additional 3 h. After completion of the reaction, the reaction solution was washed with 1.0 mol/L hydrochloric acid; a water layer was extracted three times with ethyl acetate. The collected organic layer was washed with saturated saline, and then dried with magnesium sulfate.After drying, the mixture was subjected to suction filtration, and the filtrate was concentrated. An obtained residue was purified by silica gel column chromatography (hexane aseluent), and an obtained solution was concentrated. The residue solid was recrystallized with a mixed solvent of chloroform and hexane to yield 0.7 g of a white, powdery solid of Synthesis 20 parts of 2-iodofluorene was dissolved in a mixed solution of 114 parts of dimethyl sulfoxide (DMSO) and 23 parts of tetrahydrofuran (THF), and the thus obtained mixture was then stirred at 25C for 10 minutes. Thereafter, while stirring, 8.7 parts of potassium-tert-butoxide was added to the mixture. Twenty minutes later, 13.2 parts of methyl iodide was added to the mixture, and further twenty minutes later, 8.7 parts of potassium-tert-butoxide was added thereto. Further, twenty minutes later, 13.2 parts of methyl iodide was added thereto, and the obtained mixture was then stirred at 25C for 2 hours. After completion of the stirring, tha THF was distilled away from the reaction solution, and it was then extracted with toluene-water. The toluene phase was dried over magnesium sulfate, and the toluene was then distilled away, thereby obtaining a brown tarry solid. This brown tarry solid was separated and purified by column chromatography (hexane-ethyl acetate) to obtain 21 parts of 2-Iodo-9, 9-dimethyl-fluorene (6.9384 g, 21 mmol), freshly distilled aniline (0.9622 g, 10 mmol), 2, 2-bipyridine (178 mg, ~1 mmol), CuI (232 mg, ~1 mmol) were dissolved in 60 ml xylene, protected with Ar and heated to reflux for 48 h. After cooled to room temperature, the reaction mixture was filtered through Celite and filtrate was washed with toluene. The combined organic layer was washed with brine, dried with Na2SO4. Silica gel column chromatography using CH2Cl2/hexane (v/v=1:3) as eluent gave product as light yellow solid, which was recrystalized from CH3OH to afford colorless crystal (2.5874g), yield 56%. 1H NMR (400 MHz, CDCl3) delta = 7.63 (d, J = 7.3 Hz, 2H), 7.58 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 7.3 Hz, 2H), 7.30 (dd, J = 14.0, 7.0 Hz, 4H), 7.21 (dd, J = 13.1, 4.8 Hz, 4H), 7.05 (t, J = 7.4 Hz, 4H), 1.40 (s, 12H). MS calc: m/z 477.25 ([M+]), TOF-MS found 477.3350 ([M+]).Synthesis 20 parts of 5L round bottom flask200 g (0.73 mol) of 2-bromo-9, 9'-dimethylfluorene and 2400 ml of tetrahydrofuran were added thereto, stirred for 30 minutes under a nitrogen atmosphere, and the reaction mass was cooled to -78 C. 549 ml (0.88 mol) of 1.6 M normal butyllithium were slowly added dropwise. After stirring for 24 hours at room temperature the reaction is cooled to -78 C. After 223 g (0.88 mol) of iodine was slowly added, the temperature was raised to room temperature and the mixture was stirred for 12 hours.After completion of the reaction, the reaction was terminated with aqueous sodium thiosulfate solution, extracted, and the organic layer was concentrated under reduced pressure, and then purified by column chromatography.209 g (yield 89%) of were obtained.209 g (0.63 mol) of synthesized in Scheme 23, 122.1 g (0.789 mol) of 2-bromoaniline, 12 g of tris (dibenzideneacetone) dipalladium (0) in a 5 L round bottom flask 0.013 mol), 14.5 g (0.026 mol) of 1, 1'-bis (diphenylphosphino) ferrocene, 94.1 g (0.979 mol) of sodium tert-butoxide and 2100 ml of toluene were added and refluxed for 12 hours. After completion of the reaction, the mixture was filtered and concentrated under reduced pressure to obtain 164 g (yield 69%) of using column chromatography.