Hydrochloric Acid → HCID 67105798, compound

HRID 239208Notes

Reaction equation

HRID 239208 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:8]2([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[C:20]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][CH:13]=3)[CH:5]=[CH:6][CH:7]=1.C([Li])CCC.[B:32](OC)([O:35]C)[O:33]C.Cl>C(OCC)(=O)C.CCCCCC.O1CCCC1>[C:20]1([C:8]2([C:9]3[CH:10]=[C:11]([B:32]([OH:35])[OH:33])[CH:12]=[CH:13][CH:14]=3)[C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][C:26]=3[C:3]3[C:4]2=[CH:5][CH:6]=[CH:7][CH:2]=3)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 582335499-(3-Bromophenyl)-9-phenyl-9H-fluoreneHCID 178418339Butyllithium

Product 1

HCID 67105798HCID 67105798, compoundYield 92%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

In a 100 mL three-neck flask was put 1.4 g (3.6 mmol) of 9-(3-bromophenyl)-9-phenyl-9H-fluorene. The air in the flask was replaced with nitrogen. Then, 36.0 mL of tetrahydrofuran was added to the mixture, and the mixture was stirred at 80° C. for 30 minutes. After the stirring, 2.4 mL (4.0 mmol) of a 1.65 mol/L hexane solution of n-butyllithium was dripped with a syringe, followed by stirring at −80° C. for 2 hours. Then, 0.6 mL (4.8 mmol) of trimethyl borate was added, and the mixture was stirred overnight while the temperature thereof was gradually increased from −80° C. to room temperature. After the stirring, an aqueous solution of hydrochloric acid (1 mol/L) was added to this mixture, and it was then stirred at room temperature for 30 minutes. Then, ethyl acetate was added to separate the organic layer and the aqueous layer of this mixture, and the aqueous layer was extracted with ethyl acetate three times. This ethyl acetate layer and the organic layer were combined, washed with saturated brine, and dried with magnesium sulfate. The obtained mixture was gravity filtered so that magnesium sulfate was removed, and the obtained filtrate was concentrated to give a white solid. Recrystallization of the obtained white solid from a mixed solvent of ethyl acetate and hexane gave 1.2 g of a white solid in 90% yield, which was the substance to be produced. The synthesis scheme of this Step 1 is shown in (E18-1) given below.

Workup

  1. customIn a 100 mL three-neck flask was put
  2. stirringby stirring at −80° C. for 2 hours
  3. stirringthe mixture was stirred overnight while the temperature
  4. temperaturethereof was gradually increased from −80° C. to room temperature
  5. stirringwas then stirred at room temperature for 30 minutes
  6. customto separate the organic layer
  7. extractionthe aqueous layer of this mixture, and the aqueous layer was extracted with ethyl acetate three times
  8. washwashed with saturated brine
  9. dry with materialdried with magnesium sulfate
  10. filtrationfiltered so that magnesium sulfate
  11. customwas removed
  12. concentrationthe obtained filtrate was concentrated
  13. customto give a white solid
  14. customRecrystallization of the obtained white solid from a mixed solvent of ethyl acetate and hexane

Sources & evidence

ORD record
ord-d0078ebdd5fc4bc3818924ca44c4e28c
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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