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

HRID 1244084노트

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HRID 1244084 반응식
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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-80888f35e5354c14bd79626bec9237b3
출처 데이터셋
uspto-grants-2006_10
특허 번호
US07119360B2

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