Iodine → HCID 66986610, compound

A dry 250 mL three-neck flask was charged with small Mg turnings (2.80 g, 118 mmol) followed by anhydrous THF (100 mL). A few iodine crystals were added and the heterogeneous mixture was heated at reflux for 15 minutes and then cooled to room temperature. Stirring was stopped and 1,2-dibromoethane (0.25 mL) was added to the reaction vessel. After 5 minutes an exothermic reaction ensued and stirring was resumed for 20 minutes. The reaction was then cooled to 20° C. and bromo-(4-hexyloxy)-benzene (27.8 g, 108 mmol) was added over a period of an hour while keeping the temperature between 14-18° C. The cooling bath was removed and the reaction was stirred for an additional 10 minutes as the temperature of the reaction rose to 28° C. The reaction was cooled to room temperature and the contents were transferred by pipette to a stirred toluene (250 mL) suspension of 2,7,-dibromofluorenone (30.0 g, 90.4 mmol) that was maintained at −10° C. with a cooling bath. The cooling bath was removed and the reaction mixture was stirred at room temperature for 20 minutes and subsequently treated with 20 mL of EtOH and a saturated solution of NH4Cl (5 mL). The reaction mixture was filtered to remove insoluble materials and transferred to a separatory funnel containing EtOAc (100 mL) and H2O (100 mL). The layers were separated and the organic layer was washed with H2O (2×100 mL), brine (1×100 mL), and dried over MgSO4. The solvents were removed to dryness to give a crude yellow solid (50.8 g). The crude material was recrystallized from hexane/CH2Cl2 to afford the product (9-(4-Hexyloxyphenyl)-9H-fluoren-9-ol) as an off-white microcrystalline material. Yield: 38.6 g, 79%. 1H NMR (500 MHz, CD2Cl2, 25° C.) δ 0.91 (t, 3H), 1.32 (m, 4H), 1.41 (m, 2H), 1.74 (m, 2H), 2.66 (s, 1H), 3.92 (t, 2H), 6.79 (d, 2H), 7.23 (d, 2H), 7.43 (d, 2H), 7.52 (m, 4H).

1. temperaturethe heterogeneous mixture was heated
2. temperatureat reflux for 15 minutes
3. customAfter 5 minutes an exothermic reaction
4. stirringstirring
5. temperatureThe reaction was then cooled to 20° C.
6. custombetween 14-18° C
7. customThe cooling bath was removed
8. stirringthe reaction was stirred for an additional 10 minutes as the temperature of the reaction
9. customrose to 28° C
10. temperatureThe reaction was cooled to room temperature
11. temperaturewas maintained at −10° C. with a cooling bath
12. customThe cooling bath was removed
13. stirringthe reaction mixture was stirred at room temperature for 20 minutes
14. additionsubsequently treated with 20 mL of EtOH
15. filtrationThe reaction mixture was filtered
16. customto remove insoluble materials
17. customtransferred to a separatory funnel
18. additioncontaining EtOAc (100 mL) and H2O (100 mL)
19. customThe layers were separated
20. washthe organic layer was washed with H2O (2×100 mL), brine (1×100 mL)
21. dry with materialdried over MgSO4
22. customThe solvents were removed to dryness
23. customto give a crude yellow solid (50.8 g)
24. customThe crude material was recrystallized from hexane/CH2Cl2

ORD record

ord-3f096649fbd74860af9888729e867db0

Source dataset

uspto-grants-2013_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08512879B2