Furan → 6,7-Difluoro-1,4-epoxy-1,4-dihydronaphthalene

HRID 28787

반응식

HRID 28787 반응식
[F:1][C:2]1[C:3](Br)=[C:4](Br)[CH:5]=[CH:6][C:7]=1[F:8].[O:11]1[CH:15]=[CH:14][CH:13]=[CH:12]1.[Li]CCCC>CCOCC>[F:1][C:2]1[CH:3]=[C:4]2[C:5](=[CH:6][C:7]=1[F:8])[CH:15]1[O:11][CH:12]2[CH:13]=[CH:14]1

참가 물질

5

반응물 3

HCID 8029FuranHCID 178017571,2-Dibromo-3,4-difluorobenzeneHCID 178418339Butyllithium

생성물 1

HCID 120370736,7-Difluoro-1,4-epoxy-1,4-dihydronaphthalene수율 70%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

반응 조건

온도
-78 °C

실험 절차

To 3,4-difluoro-1,2-dibromo-benzene (0.75 g, 2.78 mmol) and furan (1 mL, 14.7 mmol) in Et2O (15 mL) at −78° C. was added BuLi (1.1 mL, 2.5M in hexanes, 2.75 mmol) dropwise. The reaction was stirred for two hours at −78° C. and then was allowed to warm to room temperature. After 2 hours, the reaction mixture was quenched with water dropwise and then was poured into water. The organic layer was separated and the aqueous layer was extracted three times with Et2O. The combined organic layers were washed with brine, dried over MgSO4, concentrated and chromatographed (25% ethyl acetate:hexanes) on silica gel to give 24 (350 mg, 70%) as a colourless oil. Rf=0.21 on silica gel (20% ethyl acetate:hexanes); bp 40° C. @ 0.5 mmHg]; IR (neat, cm−1), 3017 (M), 1624 (s), 1465 (s), 1365 (s), 1253 (s), 1190 (m), 1040 (s), 857 (s). 1H NMR (400Mz, CDCl3) δ 7.06 (2H, dd, JH-F=7.7, 7.7 Hz), 7.01 (2H, s), 5.67 (2H, s); 13C NMR (400 MHz, CDCl3) δ 147.2 (dd, JC-F=247.9, 14.5 Hz), 145.1 (dd, JC-F=4.3, 4.3 Hz), 143.1, 110.8 (m), 82.1.HRMS calcd for C10H6O (M+): 180.0387. Found: 180.0394.

후처리

  1. temperatureto warm to room temperature
  2. waitAfter 2 hours
  3. customthe reaction mixture was quenched with water dropwise
  4. additionwas poured into water
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was extracted three times with Et2O
  7. washThe combined organic layers were washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customchromatographed (25% ethyl acetate:hexanes) on silica gel

출처 및 근거

ORD 기록
ord-03ec4bc8ab4d42e0a9f5cc31b1c8b69c
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07420003B2

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