Triphenylphosphine → 2-Bromo-1-(3-fluorobenzyloxy)-4-nitrobenzene

HRID 6816

반응식

HRID 6816 반응식
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[OH:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:31][C:32]1[CH:33]=[C:34]([CH:37]=[CH:38][CH:39]=1)[CH2:35]O.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.O.CCOC(C)=O>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][CH2:35][C:34]1[CH:37]=[CH:38][CH:39]=[C:32]([F:31])[CH:33]=1

참가 물질

8

반응물 4

HCID 11776TriphenylphosphineHCID 221092-Bromo-4-nitrophenolHCID 680083-Fluorobenzylic alcoholHCID 5363146Diisopropyl azodicarboxylate

생성물 1

HCID 218748002-Bromo-1-(3-fluorobenzyloxy)-4-nitrobenzene수율 68%

시약·촉매·용매 3

HCID 962Water용매HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

반응 조건

온도
0 °C

실험 절차

2-Bromo-4-nitrophenol (4.86 g, 0.0223 mol), triphenylphosphine (7.6 g, 0.0290 mol), 3-fluorobenzylalcohol (3.65 g, 0.0290 mol) were combined and dissolved in THF (89 mL). The reaction temperature was cooled to 0° C. and DIAD (4.50 g, 0.0290 mol) was added. The reaction was allowed to warm slowly to rt and stirred for 3 h before it was diluted with water (100 mL) and EtOAc (100 mL). The layers were separated and the aqueous layer was extracted with EtOAc (200 mL×2). The organic extracts were combined and washed with brine, followed by drying over sodium sulfate. The volatiles were removed in vacuo and the residual semi-solid was treated with diethyl ether. The solids were removed by filtration. The volatiles from the resulting filtrate were removed in vacuo and the material was purified using EtOAc:Hexanes (90/10) in a biotage LC system to afford the title compound as a yellow solid (3.73 g, 68% yield). 1H NMR (DMSO-d6) □ 8.43 (d, 1H); 8.26 (m, 1H); 7.45 (m, 1H); 7.38 (d, 1H); 7.30 (m, 2H); 7.17 (m, 1H); 5.39 (s, 2H).

후처리

  1. temperatureto warm slowly to rt
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with EtOAc (200 mL×2)
  4. washwashed with brine
  5. dry with materialby drying over sodium sulfate
  6. customThe volatiles were removed in vacuo
  7. additionthe residual semi-solid was treated with diethyl ether
  8. customThe solids were removed by filtration
  9. customThe volatiles from the resulting filtrate were removed in vacuo
  10. customthe material was purified

출처 및 근거

ORD 기록
ord-1aa64b4167fe4b359e015b9b3ca05d8f
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07084147B2

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