N,N-二乙基苯胺 → Methyl 4-hydroxy-3-(1-vinylcyclopentyl)benzoate

HRID 1662467笔记

反应方程式

HRID 1662467 反应方程式
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

参与物

5

反应物 3

HCID 7061N,N-二乙基苯胺HCID 6913588N,O-双三甲硅基乙酰胺HCID 57467652Methyl 4-(2-cyclopentylideneethoxy)benzoate

产物 1

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

试剂、催化剂与溶剂 1

HCID 3283乙醚溶剂

反应条件

温度
240 °C

实验过程

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)+.

后处理

  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)

来源与证据

ORD记录
ord-4fd529074b8f4bd288eb4b50cd770a5f
来源数据集
uspto-grants-2011_10
专利号
US08030354B2

反应笔记

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