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

HRID 2174432ノート

反応式

HRID 2174432 の反応式
[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

参加物

8

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 3283Diethyl Ether溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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;

後処理

  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

出典と根拠

ORDレコード
ord-8dacbd41a0434bf8b1a441739900ca14
出典データセット
uspto-grants-2015_06
特許番号
US09061981B2

反応ノート

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