Chlorotrimethylsilane → (7-Bromo-9,9-dioctyl-9H-fluoren-2-yl)(trimethyl)silane

HRID 1244084Notes

Reaction equation

HRID 1244084 reaction equation
C([Li])CCC.CCCCCC.[Br:12][C:13]1[CH:25]=[CH:24][C:23]2[C:22]3[C:17](=[CH:18][C:19](Br)=[CH:20][CH:21]=3)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=2[CH:14]=1.Cl[Si:44]([CH3:47])([CH3:46])[CH3:45]>C1COCC1>[Br:12][C:13]1[CH:25]=[CH:24][C:23]2[C:22]3[C:17](=[CH:18][C:19]([Si:44]([CH3:47])([CH3:46])[CH3:45])=[CH:20][CH:21]=3)[C:16]([CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH3:42])([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])[C:15]=2[CH:14]=1

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8058HexaneHCID 52153212,7-Dibromo-9,9-di-n-octylfluoreneHCID 178418339Butyllithium

Product 1

HCID 21932312(7-Bromo-9,9-dioctyl-9H-fluoren-2-yl)(trimethyl)silane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-Butyllithium in hexane (6.0 mL, 1.6 M, 9.6 mmol) was added to a solution of 2,7-dibromo-9,9-di-n-octylfluorene (7) (5.00 g, 9.13 mmol) in dry THF (50 mL) in a schlenk flask at −78° C. and the mixture was stirred for 20 minutes. Then chlorotrimethylsilane (1.5 mL, 1.29 g, 1.3 equiv) was added and the reaction was allowed to slowly warm to room temperature. The mixture was stirred overnight and the reaction was quenched with saturated brine. The product was extracted into diethyl ether, and the extract was washed with brine and dried over MgSO4. The crude product was chromatographed on silica using hexane as eluent to give 2-bromo-7-trimethylsilyl-9,9-di-n-octylfluorene as a colourless oil, (3.50 g, 71%). n-Butyllithium in hexane (4.4 mL, 1.6 M, mmol) was added to a solution of 2-bromo-7-trimethylsilyl-9,9-di-n-octylfluorene (3.47 g, 6.41 mmol) in dry THF (75 mL) in a schlenk flask at −78° C., and the mixture was stirred for 20 minutes. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.44 mL, 1.31 g, 7.04 mmol) was added and the reaction was stirred for 24 h after warming to room temperature. The reaction was then quenched with brine, and the product was extracted into diethyl ether. The extract was washed with brine and dried over MgSO4. The crude product was chromatographed on silica using 0–3% ethylacetate in hexane as eluent, to give 8 as a colourless solid (2.67 g, 71%). 1H NMR (CD2Cl2): δ 7.73 (m, 4H) 7.51 (m, 2H) 1.99 (t, 4H, J=8.2 Hz) 1.36–0.54 (m, 42H) 0.31 (s, 9H)ppm. 13C NMR: δ 151.60, 151.34, 149.76, 145.29, 142.69, 141.07, 134.71, 133.01, 130.08, 129.03, 120.50, 120.25, 84.93, 56.22, 41.26, 33.01, 32.84, 31.11, 30.37, 25.98, 24.95, 23.85, 15.08, 0.01. FDMS m/z 588.90.

Workup

  1. stirringThe mixture was stirred overnight
  2. customthe reaction was quenched with saturated brine
  3. extractionThe product was extracted into diethyl ether
  4. washthe extract was washed with brine
  5. dry with materialdried over MgSO4
  6. customThe crude product was chromatographed on silica

Sources & evidence

ORD record
ord-80888f35e5354c14bd79626bec9237b3
Source dataset
uspto-grants-2006_10
Patent number
US07119360B2

Reaction notes

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