Acetic Anhydride → HCID 86722421、化合物

HRID 718810

反応式

HRID 718810 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:14])[CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[CH:4][C:3]=1[N+:15]([O-])=O.[C:18](OC(=O)C)(=[O:20])[CH3:19]>[Pd].CCOC(C)=O>[C:18]([NH:15][C:3]1[CH:4]=[C:5]([C:8](=[O:14])[CH2:9][CH2:10][C:11]([OH:13])=[O:12])[CH:6]=[CH:7][C:2]=1[CH3:1])(=[O:20])[CH3:19]

参加物

5

反応物 2

HCID 7918Acetic AnhydrideHCID 821168284-(4-Methyl-3-nitrophenyl)-4-oxobutanoic acid

生成物 1

HCID 86722421HCID 86722421、化合物収率 76%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 8857Ethyl Acetate溶媒

実験手順

10% Pd/C (100 g) was added to a solution of 4-(4-methyl-3-nitrophenyl)-4-oxobutanoic acid (73) (3.40 kg, 14.3 mol) and EtOAc (20 L) in 40 L Parr reactor. Acetic anhydride (2.40 L, 25.4 mol) was added. The mixture was stirred under about 5 bar H2 atmosphere overnight. The reaction was concentrated under reduced pressure. To the resulting grey solid was added EtOH (14 L) and H2SO4 (˜35 mL). The mixture was stirred in the 40 L Parr vessel under about 5 bar H2 pressure overnight at rt. The reaction mixture was poured into 2 N aqueous NaOH (35 L), stirred overnight at rt, and then filtered through of Celite® rinsing with water. The filtrate and washings were combined and concentrated under reduced pressure to remove EtOH. The aqueous residue was washed with tert-butyl methyl ether (7 L). The aqueous layer was acidified with 2 N aq. HCl. The precipitate was collected by filtration rinsing with water (2×14 L) and dried to afford 4-(3-acetamido-4-methylphenyl)-4-oxobutanoic acid (74) (2.70 kg, 76% yield). 1H NMR (300 MHz, DMSO): δ 12.03 (s, 1H), 9.25 (s, 1H), 7.50 (s, 1H), 7.30 (d, J=7.6 Hz, 2H), 6.88 (d, J=7.6 Hz, 2H), 2.56 (m, 2H), 2.28 (m, 2H), 2.16 (s, 3H), 2.04 (s, 3H), 1.74 (m, 2H).

後処理

  1. concentrationThe reaction was concentrated under reduced pressure
  2. additionTo the resulting grey solid was added EtOH (14 L) and H2SO4 (˜35 mL)
  3. stirringThe mixture was stirred in the 40 L Parr vessel under about 5 bar H2 pressure overnight at rt
  4. additionThe reaction mixture was poured into 2 N aqueous NaOH (35 L)
  5. stirringstirred overnight at rt
  6. filtrationfiltered through of Celite®
  7. washrinsing with water
  8. concentrationconcentrated under reduced pressure
  9. customto remove EtOH
  10. washThe aqueous residue was washed with tert-butyl methyl ether (7 L)
  11. filtrationThe precipitate was collected by filtration
  12. washrinsing with water (2×14 L)
  13. customdried

出典と根拠

ORDレコード
ord-9e1a616dc9e44916b08cf385d1fe0f8d
出典データセット
uspto-grants-2015_11
特許番号
US09193744B2

関連ノート

読み込み中…