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

HRID 1662467

반응식

HRID 1662467 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>CCOCC>[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

A mixture of methyl 4-(2-cyclopentylideneethoxy)benzoate 66.67B (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, ether (60 mL) was added, and the mixture 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 stirred at room temperature for 30 minutes. Ether (80 mL) was added, and the mixture was washed with NaHCO3 (30 mL) and brine (15 mL). The organic layer was dried over MgSO4. After filtering, the solvent was removed. The residue was purified by Combi Flash silica gel column, eluting with hexane/EtOAc (95/5) to give the compound 66.67C, (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 mixture 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. additionEther (80 mL) was added
  8. washthe mixture was washed with NaHCO3 (30 mL) and brine (15 mL)
  9. dry with materialThe organic layer was dried over MgSO4
  10. filtrationAfter filtering
  11. customthe solvent was removed
  12. customThe residue was purified by Combi Flash silica gel column
  13. washeluting with hexane/EtOAc (95/5)

출처 및 근거

ORD 기록
ord-4fd529074b8f4bd288eb4b50cd770a5f
출처 데이터셋
uspto-grants-2011_10
특허 번호
US08030354B2

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