Hydrochloric Acid → 4-(4-(Benzyloxy)phenyl)-4-(2-fluorophenyl)cyclohex-2-enone

HRID 2174432노트

반응식

HRID 2174432 반응식
[OH-].[K+].[CH2:3]([O:10][C:11]1[CH:16]=[CH:15][C:14]([CH:17]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=2[F:26])[CH:18]=O)=[CH:13][CH:12]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH:27]([C:29]([CH3:31])=[O:30])=[CH2:28].Cl>CCO.C1COCC1.CCOCC>[CH2:3]([O:10][C:11]1[CH:12]=[CH:13][C:14]([C:17]2([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[F:26])[CH2:18][CH2:31][C:29](=[O:30])[CH:27]=[CH:28]2)=[CH:15][CH:16]=1)[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

참가 물질

8

반응물 4

HCID 313Hydrochloric AcidHCID 6570Methyl vinyl ketoneHCID 14797Potassium HydroxideHCID 894003632-(4-(Benzyloxy)phenyl)-2-(2-fluorophenyl)acetaldehyde

생성물 1

HCID 712451374-(4-(Benzyloxy)phenyl)-4-(2-fluorophenyl)cyclohex-2-enone수율 98.2%

시약·촉매·용매 3

HCID 702Ethanol용매HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매

실험 절차

A solution of KOH (110 mg, 2.0 mmol) in EtOH (3 mL) was added at 0° C. to a stirred solution of 4 (2.52 g, 7.9 mmol) and methyl vinyl ketone (0.61 g, 8.7 mmol) in THF (60 mL). The resulting mixture was stirred at room temperature overnight. Ether (200 mL) and HCl (50 mL, 10% aqueous solution) were added. The organic phase was washed with HCl (50 mL, 10% aqueous solution), H2O (50 mL), NaHCO3 (50 mL, saturated aqueous solution), dried over Na2SO4 and evaporated under reduced pressure. The crude material was dissolved in EtOH (40 mL) and HCl (2 mL, 37% aqueous solution) was added. The mixture was heated at 50° C. for 30 min under stirring. After cooling to room temperature, H2O (50 mL) was added. The mixture was extracted with diethyl ether (3×100 mL) and the combined organic phase was washed with NaHCO3 (2×50 mL, saturated aqueous solution) and brine (50 mL), dried over Na2SO4 and evaporated under reduced pressure to yield 2.89 g crude material. Purification by column chromatography (heptane:ethyl acetate 4:1 to 2:1) yielded 2.41 g, 82% as an off-white solid. 1H-NMR (CDCl3) δ; 7.44-7.35 (m, 6H), 7.35-7.28 (m, 2H), 7.17 (dt, 1H, J=7.5 Hz and 1.4 Hz), 7.11 (d, 2H, J=8.9 Hz), 7.02 (dd, 1H, J=7.0 Hz and 1.4 Hz), 6.92 (d, 2H, J=8.9 Hz), 6.19 (d, 1H, J=10.3 Hz), 5.04 (s, 2H), 2.90-2.81 (m, 1H), 2.62-2.52 (m, 1H), 2.44 (at, 2H, J=6.6 Hz); 13C-NMR (CDCl3) δ; 199.0, 161.3 (d, J=249.6 Hz), 157.9, 154.9 (d, J=3.8 Hz), 137.1 (d, J=12.1 Hz), 132.0 (d, J=10.8 Hz), 129.5 (d, J=8.8 Hz), 129.3, 128.8, 128.7 (d, J=4.2 Hz), 128.2, 128.1, 127.7, 124.3 (d, J=3.5 Hz), 117.2 (d, J=22.7), 115.0, 70.3, 47.3 (d, J=1.9 Hz), 35.1, 35.0;

후처리

  1. washThe organic phase was washed with HCl (50 mL, 10% aqueous solution), H2O (50 mL), NaHCO3 (50 mL, saturated aqueous solution)
  2. dry with materialdried over Na2SO4
  3. customevaporated under reduced pressure
  4. dissolutionThe crude material was dissolved in EtOH (40 mL)
  5. additionHCl (2 mL, 37% aqueous solution) was added
  6. temperatureThe mixture was heated at 50° C. for 30 min
  7. stirringunder stirring
  8. temperatureAfter cooling to room temperature
  9. additionH2O (50 mL) was added
  10. extractionThe mixture was extracted with diethyl ether (3×100 mL)
  11. washthe combined organic phase was washed with NaHCO3 (2×50 mL, saturated aqueous solution) and brine (50 mL)
  12. dry with materialdried over Na2SO4
  13. customevaporated under reduced pressure

출처 및 근거

ORD 기록
ord-8dacbd41a0434bf8b1a441739900ca14
출처 데이터셋
uspto-grants-2015_06
특허 번호
US09061981B2

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