N,N-Diethylaniline → Methyl 4-hydroxy-3-(1-vinylcyclopentyl)benzoate

HRID 404389

반응식

HRID 404389 반응식
C1(=CC[O:8][C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=2)CCCC1.C(N(CC)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)C.[CH3:30]/C(/O[Si](C)(C)C)=N\[Si](C)(C)C>C(OCC)C>[OH:8][C:9]1[CH:10]=[CH:11][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:17][C:18]=1[C:26]1([CH:27]=[CH2:22])[CH2:25][CH2:24][CH2:23][CH2:30]1

참가 물질

5

반응물 3

HCID 7061N,N-DiethylanilineHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 57467652Methyl 4-(2-cyclopentylideneethoxy)benzoate

생성물 1

HCID 57467653Methyl 4-hydroxy-3-(1-vinylcyclopentyl)benzoate수율 30.5%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매

반응 조건

온도
240 °C

실험 절차

The reaction mixture of methyl 4-(2-cyclopentylideneethoxy)benzoate 26.2 (0.50 g, 2.0 mmol), N,N-diethylaniline (3.2 mL, 20 mmol) and N,O-bis(trimethylsilyl)acetamide (2.5 mL, 10 mmol) in a 20 mL seal tube was heated at 240° C. for 48 hours. The reaction was then cooled to room temperature. Diethyl ether (60 mL) was added, and the organic layer was washed with HCl (3N, 20 mL). The organic layer was separated and the solvent was removed. The residue was dissolved in MeOH (10 mL) and HCl (3N, 2 mL) and stiffed at room temperature for 30 minutes. Diethyl ether (80 mL) was added, and the organic layer was washed with NaHCO3 (30 mL) and brine (15 mL). The organic layer was dried over MgSO4. After filtration, the solvent was removed, and the residue was purified by CombiFlash® silica gel column chromatography, eluting with hexane/EtOAc, 95/5 to give 26.3 (0.15 g, yield 30%). 1H NMR (500 MHz, CDCl3) δ ppm 7.90 (1H, d, J=2.2 Hz), 7.80 (1H, dd, J=8.3, 2.0 Hz), 6.81 (1H, d, J=8.3 Hz), 5.99 (1H, dd, J=17.6, 10.5 Hz), 5.77 (1H, s), 5.18 (1H, dd, J=10.5, 1.0 Hz), 5.08 (1H, d, J=17.6 Hz), 3.82 (3H, s), 1.89-2.03 (4H, m), 1.56-1.78 (4H, m). MS ESI (neg.) m/e: 245.1 (M−H)+.

후처리

  1. customseal tube
  2. temperatureThe reaction was then cooled to room temperature
  3. washthe organic layer was washed with HCl (3N, 20 mL)
  4. customThe organic layer was separated
  5. customthe solvent was removed
  6. dissolutionThe residue was dissolved in MeOH (10 mL)
  7. additionDiethyl ether (80 mL) was added
  8. washthe organic layer was washed with NaHCO3 (30 mL) and brine (15 mL)
  9. dry with materialThe organic layer was dried over MgSO4
  10. filtrationAfter filtration
  11. customthe solvent was removed
  12. customthe residue was purified by CombiFlash® silica gel column chromatography
  13. washeluting with hexane/EtOAc, 95/5

출처 및 근거

ORD 기록
ord-4a9bd7ebdd48484a98d468d14f5d1049
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08748462B2

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