9,9-diMethyl-N-phenyl-9H-fluoren-2-aMine

Tri-tert-butylphosphine (2.7 ml of a 1.0 M solution in toluene, 2.7 mmol), palladium acetate (307 mg, 1.4 mmol) and sodium tert-butoxide (9.8 g, 102 mmol) are added to a solution of phenyl-(9, 9-dimethyl-9H-fluoren-2-yl)-amine (20.5 g, 71 mmol) and 4-bromo-9, 9’-spirobifluorene (27 g, 68 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, extended withtoluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhiet extractor (toluene) and purified by zone sublimation in vacuo twice (p = 3 x 10-a mbar, T = 298°C). The product is isolated in the form of a pale-yellow solid (8 g, 20 percent of theory, purity > 99.99percentaccording to HPLC).8.2 g (30 mmol) of 2-bromo-9, 9-dimethylfluorene, 4.1 mL (45 mmol) of aniline, 4.3 g (45 mmol) of t-BuONa, 0.55 g (0.6 mmol) of Pdtri -tert-butylphosphine (3 mL of 1.0 M in toluene, 7.32 mmol), palladium acetate (0.4 g, 1.83 mmol) and sodium tert-butoxide (22.8 g, 238 mmol) was added to aniline (17.0 g, 183 mmol) and 2-bromo-9, 9-dimethylfluorene (49.7 g, 183 mmol) in degassed toluene (500 mL), and the mixture was heated under reflux for 2 hours. The reaction was mixed The mixture was cooled to room temperature, diluted with toluene and filtered through celite. The filtrate was diluted with water and extracted with toluene And the organic phase was combined and evaporated under vacuum. The residue was filtered through silica gel (heptane / dichloromethane) And crystallized from isopropanol. A solid form of A2 (45.3 g, theoretical 87percent) was obtained.Reactor 2-bromo -9, 9-dimethyl -9H-fluorene (1.37g, 5mmol), aniline (0.93g, 10 mmol), PdSynthesis Synthesis of Intermediate 6 1.21 g (13 mmol) of phenylamine, 2.73 g (10 mmol) of 9, 9'-dimethyl-2-bromofluorene, 1.44 g (15 mmol) of t-BuONa, 183 mg (0.2 mmol) of PdExamples Synthesis Example: Synthesis of Compound 11 [Show Image] Synthesis of Intermediate 1 27.3 g (100.0 mmol) of 2-bromo-9, 9-dimethylfluorene, 11.2 g (120.0 mmol) of aniline, 14.4 g (150.0 mmol) of NaOt-Bu, 4.5 g (5.0 mmol) of PdUnder an argon atmosphere, a mixture of 15 g (54.9 mmol) of 2-bromo-9, 9-dimethylfluorene, 5 mL (54.9 mmol) of aniline, 0.754 g (0.82 mol) of tris(dibenzylideneacetone) dipalladium(0), 1.02 g (1.64 mmol) of 2, 2′-bis(diphenylphosphino)-1, 1′-binaphthyl (BINAP), and 10.5 g (109.3 mmol) of sodium t-butoxide in 270 mL of toluene was stirred and refluxed for 7 h under heating. (0258) After the reaction, the mixture was cooled to room temperature and extracted with ethyl acetate in a separatory funnel. The obtained organic layer was washed with a sodium carbonate aqueous solution, dried over anhydrous sodium sulfate, filtered, and then concentrated. The obtained residue was purified by silica gel column chromatography and recrystallization to obtain 12 g (yield: 77percent) of solid, which was identified as the following intermediate 18 by FD-MS analysis.In a 250 ml three-neck flask, under the protection of nitrogen, add 0.01 mol of raw material O1, 0.012 mol of raw material P1, 150 mlAfter stirring and mixing with toluene, 5×10-5 mol of Pd2(dba)3, 5×10-5 mol of P(Ph)3, and 0.03 mol of sodium tert-butoxide were added. The mixture was heated to 105° C. and refluxed for 24 hours. Residue of bromine was left, the reaction was complete; it was naturally cooled to room temperature, filtered, and the filtrate was rotary-distilled to a fraction-free, neutral silica gel column to obtain the target product intermediate B1; HPLC purity 99.53percent, yield 75.5percent;15.0 g of the above 2-bromo-9, 9-dimethyl-9H-fluorene, 5.6 g of aniline, 7.9 g of t-BuONa, 32.0 g of Pd2 (dba) and 2.5 ml of (t-Bu) 3P were dissolved in 200 ml of toluene, and the mixture was stirred under reflux. After the reaction was confirmed by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and recrystallized to obtain 11.75 g (yield 75percent) of OP1.In a round-bottomed flask, 10.0 g of 2-bromo-9, 9-diphenyl-9H-fluorene, 3.8 g of aniline, 5.3 g of t-BuONa, and 1.4 g of Pd2 (dba) were dissolved in 150 ml of toluene. After 3 and 1.6 ml of (t-Bu)3P was stirred at reflux. The reaction was confirmed by thin layer chromatography, and after addition of water, the reaction was completed. The organic layer was extracted with dichloromethane (MC) and filtered under reduced pressureAfter that, column purification and recrystallization were performed to obtain 7.73 g (yield of 74percent) of OP1.Under the protection of argon gas, the 2-bromo -9, 9-dimethylfluorene 8.19g (30mmol), aniline 4.18g (45mmol), tertiary butyl alcohol sodium 3.60g, toluene 30 ml are sequentially into the 100 ml reaction flask. After mixing, palladium acetate is added to the reaction vial 0.03g and 1, 1 '-bis (di-tert- butyl phosphine ) ferrocene (D(t-Bu)PF) 0.07g, controlling the reaction temperature 90 °C reaction, HPLC detection reaction is ended. Adding 40 ml of water the end of the reaction, filtration, the organic layer the water washing, drying by anhydrous sodium sulfate, activated carbon decolourizations, filtering, the filtrate under reduced pressure to recover part of toluene-hexane, cooling, filtering, drying to obtain the kind of white solid 6.20g, content 99.3percent (HPLC), the yield is 72.1percent. Product melting point: 98.0-100 °C. 250ml of four bottles, Under an atmosphere of nitrogen gas, 27.3 g (0.1 M) of 2-bromo-9, 9-dimethyl) fluorene were added, 9.3 g (0. O) Aniline, 11.52 g (0.12 M sodium tert-butoxide, 0.7 g of palladium acetate, 0.5 g of CXA (n-butyl-bis (1-adamantyl) phosphine), 200ml toluene, heating reflux 6 hours, sample plate, the reaction completely. (Intermediate a: N-phenyl-9H-9, 9-dimethylfluoren-3-amine) to obtain 20.4 g of a light yellow solid (purity 99.12percent). 71.6percentSub 2-1-1 (1.9g, 20mmol), Sub 2-2-1 (5.5g, 20mmol) in a round bottom flask, Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), were added to toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100°C. The resulting organic was dried over MgSO4 and the organic layer was extracted with ether and recrystallized with water, and concentrated to silicagel column Sub 2-8, 5.2g (yield: 64percent) was obtained.

Molecular Weight:285.4
XLogP3:6
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:285.151749610
Monoisotopic Mass:285.151749610
Topological Polar Surface Area:12
Heavy Atom Count:22
Complexity:381
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes