Hydrochloric Acid → 2-Bromo-9,9-dioctyl-7-hydroxyfluorene

HRID 1243256Notes

Reaction equation

HRID 1243256 reaction equation
C([Li])CCC.[Br:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13](Br)=[CH:14][CH:15]=3)[C:10]([CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:9]=2[CH:8]=1.C[O:38]B(OC)OC.Cl>O1CCCC1>[Br:6][C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][C:13]([OH:38])=[CH:14][CH:15]=3)[C:10]([CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH3:36])([CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:9]=2[CH:8]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 52153212,7-Dibromo-9,9-di-n-octylfluoreneHCID 178418339Butyllithium

Product 1

HCID 219245182-Bromo-9,9-dioctyl-7-hydroxyfluoreneYield 45%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

2.5M n-butyllithium in hexanes (20.0 cm3, 0.05 mol) was added dropwise to a solution of 2,7-dibromo-9,9-dioctylfluorene (20.0 g, 0.0364 mol) and tetrahydrofuran (300 cm3) maintaining a temperature of −70° C. After stirring for 1 h, trimethylborate (9.45 g, 0.09 mol) was added dropwise. After allowing the solution to reach RT, 20% hydrochloric acid (100 cm3) was added and the solution stirred for a further 1.5 h. The product was extracted into diethyl ether (2×100 cm3) and the combined extracts washed with water (2×100 cm3), dried (MgSO4) and concentrated to a pale yellow oil. Diethyl ether (200 cm3) and hydrogen peroxide (30%, 100 cm3) were added and the solution heated under gentle reflux for 2.5 h with vigorous stirring. The ether layer was separated off and the aqueous layer extracted into diethyl ether (3×50 cm3). The combined organic layers were washed with saturated sodium metabisulphite solution (2×100 cm3), dried (MgSO4), filtered and evaporated down under slightly reduced pressure to a pale yellow oil, which was purified by column chromatography [silica gel, dichloromethane:hexane:ethanol 50:50:1] and recrystallisation from hexane to yield a white crystalline solid (yield 7.80 g, 45%), GC: 99%, mpt 110° C.

Workup

  1. customto reach RT
  2. stirringthe solution stirred for a further 1.5 h
  3. extractionThe product was extracted into diethyl ether (2×100 cm3)
  4. washthe combined extracts washed with water (2×100 cm3)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated to a pale yellow oil
  7. additionDiethyl ether (200 cm3) and hydrogen peroxide (30%, 100 cm3) were added
  8. temperaturethe solution heated
  9. temperatureunder gentle reflux for 2.5 h with vigorous stirring
  10. customThe ether layer was separated off
  11. extractionthe aqueous layer extracted into diethyl ether (3×50 cm3)
  12. washThe combined organic layers were washed with saturated sodium metabisulphite solution (2×100 cm3)
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. customevaporated down under slightly reduced pressure to a pale yellow oil, which
  16. customwas purified by column chromatography [silica gel, dichloromethane:hexane:ethanol 50:50:1] and recrystallisation from hexane

Sources & evidence

ORD record
ord-f78ea9f396dc4bd9be44fcdb3c75d4b6
Source dataset
uspto-grants-2006_10
Patent number
US07118787B2

Reaction notes

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