Triisopropyl borate → 2-Dihydroxyboranyl-9,9-dioctylfluorene

HRID 1828616

Reaction equation

HRID 1828616 reaction equation
[Li]CCCC.Br[C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])([CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27])[C:9]=2[CH:8]=1.[B:36](OC(C)C)([O:41]C(C)C)[O:37]C(C)C>C1COCC1>[CH2:20]([C:10]1([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[C:9]2[CH:8]=[C:7]([B:36]([OH:41])[OH:37])[CH:19]=[CH:18][C:17]=2[C:16]2[C:11]1=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

5

Reactant 3

HCID 21531Triisopropyl borateHCID 129646932-Bromo-9,9-di-n-octylfluoreneHCID 178418339Butyllithium

Product 1

HCID 111338442-Dihydroxyboranyl-9,9-dioctylfluoreneYield 89.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-BuLi (2.5 M in hexane, 12.0 mL, 30.0 mmol) is slowly added to a solution of 2-bromo-9,9-bis(n-octyl)fluorene (12.0 g, 25.6 mmol) in anhydrous THF (50 mL) at −78° C. At this temperature, the reaction mixture is stirred for 1 h before adding tri-iso-propyl borate (9.0 mL, 7.34 g, 39.0 mmol). The resulting mixture is then warmed to room temperature, stirred overnight followed by quenching with 100 mL HCl (2.0 M), and poured into a large amount of water. After extraction with ethyl ether three times, the organic portions are washed with brine before drying over anhydrous MgSO4. Solid residues collected by evaporating off the solvent are purified by column chromatography on silica gel with petroleum ether/ethyl acetate (2:1) to yield 9,9-bis(n-octyl)fluoren-2-yl-boronic acid (2a) as a white solid (10.0 g, 89%).

Workup

  1. stirringstirred overnight
  2. customby quenching with 100 mL HCl (2.0 M)
  3. additionpoured into a large amount of water
  4. extractionAfter extraction with ethyl ether three times
  5. washthe organic portions are washed with brine
  6. dry with materialbefore drying over anhydrous MgSO4
  7. customSolid residues collected
  8. customby evaporating off the solvent
  9. customare purified by column chromatography on silica gel with petroleum ether/ethyl acetate (2:1)

Sources & evidence

ORD record
ord-68777ddcb6944665a0fb1e3ae2307484
Source dataset
uspto-grants-2006_06
Patent number
US07057009B2

Linked notes

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