Potassium Carbonate → N-{4-[[4-(methyloxy)phenyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}acetamide

HRID 229170

反応式

HRID 229170 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:11]2[CH:16]=[CH:15][C:14]([NH:17][C:18](=[O:20])[CH3:19])=[CH:13][CH:12]=2)=O)=[CH:5][CH:4]=1.[CH3:21][C:22]1([CH3:31])[CH2:27][C:26]([CH3:29])([CH3:28])[CH2:25][C:24](=O)[CH2:23]1.C([O-])([O-])=O.[K+].[K+]>C1COCC1.[Zn].Cl[Ti](Cl)(Cl)Cl>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9](=[C:24]2[CH2:25][C:26]([CH3:29])([CH3:28])[CH2:27][C:22]([CH3:31])([CH3:21])[CH2:23]2)[C:11]2[CH:16]=[CH:15][C:14]([NH:17][C:18](=[O:20])[CH3:19])=[CH:13][CH:12]=2)=[CH:5][CH:4]=1

参加物

7

反応物 3

HCID 11430Potassium CarbonateHCID 843993,3,5,5-TetramethylcyclohexanoneHCID 13499420N-[4-(4-Methoxybenzoyl)phenyl]acetamide

生成物 1

HCID 68654481N-{4-[[4-(methyloxy)phenyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenyl}acetamide収率 93.2%

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 24193Titanium Tetrachloride触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a stirred suspension of zinc powder (0.39 g, 5.94 mmol) in THF (15 mL) was slowly added TiCl4 (0.33 mL, 2.97 mmol) via syringe at RT under a nitrogen atmosphere. The mixture was heated at reflux for 2 h. A solution of N-(4-{[4-(methyloxy)phenyl]carbonyl}phenyl)acetamide (56) (0.20 g, 0.74 mmol) and 3,3,5,5-tetramethylcyclohexanone (0.35 g, 2.23 mmol) in THF (4 mL) was added to the mixture. The reaction mixture was heated at reflux with stirring under a nitrogen atmosphere for 1 h. The reaction mixture was allowed to cool to room temperature. To the reaction mixture was slowly added 10% aqueous K2CO3 (15 mL). The reaction mixture was filtered through a pad of Celite and the pad was washed with EtOAc (100 mL). The filtrate was transferred to a separatory funnel and the layers were separated. The aqueous layer was further extracted with EtOAc (25 mL). The combined organic phase was washed with water, brine, dried (Na2SO4) filtered, and the filtrate was concentrated to give the crude product as yellow oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 40% EtOAc:hexanes to give 0.27 g (93%) of compound 57 as colorless viscous oil. 1H NMR (400 MHz, CDCl3): δ 0.91 (s, 6H), 0.92 (s, 6H), 1.27 (s, 2H), 1.96 (s, 2H), 1.97 (s, 2H), 2.16 (s, 3H), 3.78 (s, 3H), 6.80 (d, J=8.6 Hz, 2H), 7.06 (d, J=8.8 Hz, 2H), 7.10 (d, J=8.5 Hz, 2H), 7.39 (d, J=8.5 Hz, 2H). LCMS (ESI): m/z 392 (M+H)+, 390 (M−H)−.

後処理

  1. customat RT
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 2 h
  4. temperatureThe reaction mixture was heated
  5. temperatureat reflux
  6. filtrationThe reaction mixture was filtered through a pad of Celite
  7. washthe pad was washed with EtOAc (100 mL)
  8. customThe filtrate was transferred to a separatory funnel
  9. customthe layers were separated
  10. extractionThe aqueous layer was further extracted with EtOAc (25 mL)
  11. washThe combined organic phase was washed with water, brine
  12. dry with materialdried (Na2SO4)
  13. filtrationfiltered
  14. concentrationthe filtrate was concentrated
  15. customto give the crude product as yellow oil
  16. customThe crude product was purified by chromatography on a silica gel column
  17. washeluted with a gradient from hexanes to 40% EtOAc

出典と根拠

ORDレコード
ord-9aaed4e8867047299b93518913eb332f
出典データセット
uspto-grants-2009_07
特許番号
US07560589B2

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