(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane → 2-{5'-[6-(tert-Butyl-dimethyl-silanyloxy)-hexyl]-[2,2']bithiophenyl-5-yl}-4,4,5,5-tetramethyl-[1,3,2}dioxaborolane

HRID 644111노트

반응식

HRID 644111 반응식
[S:1]1[C:5]([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][O:12][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14])=[CH:4][CH:3]=[C:2]1[C:20]1[S:21][CH:22]=[CH:23][CH:24]=1.C([Li])CCC.[BH:30]([OH:32])[OH:31].O[C:34]([C:37](O)([CH3:39])[CH3:38])([CH3:36])[CH3:35]>C1COCC1>[C:16]([Si:13]([CH3:14])([CH3:15])[O:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]1[S:1][C:2]([C:20]2[S:21][C:22]([B:30]3[O:32][C:37]([CH3:39])([CH3:38])[C:34]([CH3:36])([CH3:35])[O:31]3)=[CH:23][CH:24]=2)=[CH:3][CH:4]=1)([CH3:18])([CH3:19])[CH3:17]

참가 물질

5

반응물 3

HCID 58807316(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilaneHCID 178418339ButyllithiumHCID 178459139HCID 178459139, 화합물

생성물 1

HCID 588073092-{5'-[6-(tert-Butyl-dimethyl-silanyloxy)-hexyl]-[2,2']bithiophenyl-5-yl}-4,4,5,5-tetramethyl-[1,3,2}dioxaborolane수율 95.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

To an ice-cooled solution of (6-[2,2′]bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane (10 g, 19.76 mmol) in anhydrous THF (150 ml) was added dropwise a solution of n-butyllithium (2.5 M in hexanes, 7.91 ml, 19.76 mmol) under nitrogen, with stirring. After 2 h, pinacol boronate (4.04 g, 21.72 mmol) was added. The ice bath was removed, and the resultant mixture was stirred overnight at room temperature. The reaction was quenched with the addition of saturated aqueous NH4Cl and the mixture extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with brine, dried over magnesium sulphate, and evaporated under reduced pressure. The residue was purified by column chromatography on silica, eluting with petroleum ether/ethyl (9:1), to give the product as a blue oil (9.52 g, 72%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.46 (d, J=3.6 Hz, 1H, Ar—H), 7.10 (d, J=3.6 Hz, 1H, Ar—H), 6.99 (d, J=3.4 Hz, 1H, Ar—H), 6.62 (d, J=3.4 Hz, 1H, Ar—H), 3.56 (t, J=6.4 Hz, 2H, OCH2), 2.73 (t, J=7.4 Hz, 2H, ArCH2), 1.21-1.70 (m, 20H, CH2 and CH3), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 145.9 (2×quat.), 144.8 (quat.), 138.0 (CH.), 134.7 (quat.), 125.0 (CH), 124.2 (CH), 124.1 (CH), 84.1 (quat.), 63.2 (OCH2), 32.8 (CH2), 31.6 (CH2), 30.2 (CH2), 28.9 (CH2), 26.0 (CH3) 25.6 (CH2), 24.8 (CH3), 18.4 (quat.), −5.2 (CH3); MS (m/e): 506 (M+, 32%), 331 (31), 305 (31), 279 (100), 261 (32), 205 (51), 83 (71).

후처리

  1. customThe ice bath was removed
  2. stirringthe resultant mixture was stirred overnight at room temperature
  3. customThe reaction was quenched with the addition of saturated aqueous NH4Cl
  4. extractionthe mixture extracted with ethyl acetate (3×70 ml)
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over magnesium sulphate
  7. customevaporated under reduced pressure
  8. customThe residue was purified by column chromatography on silica
  9. washeluting with petroleum ether/ethyl (9:1)

출처 및 근거

ORD 기록
ord-441925e5ba884816b5ed5d3453693ed5
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07700643B2

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