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2-Butenoic acid, 4-oxo-4-phenyl-, ethyl ester → 3-[[1-(carboxy)-3-phenyl-propyl]amino]-1-t-butoxycarbonylmethyl-2,3,4,5-tetrahydro-1H-benzazepin-2-one

HRID 489863
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HRID 489863 반응식
[C:1]([CH:9]=[CH:10][C:11]([O:13]CC)=[O:12])(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:16][C@H:17]1[CH2:23][CH2:22][C:21]2[CH:24]=[CH:25][CH:26]=[CH:27][C:20]=2[N:19]([CH2:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[C:18]1=[O:36].[BH4-].[Na+].C([O-])=O.[NH4+]>C1(C)C=CC=CC=1.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.[OH-].[Na+].[Pd]>[C:11]([CH:10]([NH:16][CH:17]1[CH2:23][CH2:22][C:21]2[CH:24]=[CH:25][CH:26]=[CH:27][C:20]=2[N:19]([CH2:28][C:29]([O:31][C:32]([CH3:34])([CH3:33])[CH3:35])=[O:30])[C:18]1=[O:36])[CH2:9][CH2:1][C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)([OH:13])=[O:12]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

9

반응물 4

HCID 5698852-Butenoic acid, 4-oxo-4-phenyl-, ethyl esterHCID 2723923Ammonium formateHCID 4311764Sodium borohydrideHCID 63506241,1-Dimethylethyl ((3S)-3-amino-2-oxo-2,3,4,5-tetrahydro-1H-1-benzazepin-1-yl)acetate

생성물 1

HCID 222629803-[[1-(carboxy)-3-phenyl-propyl]amino]-1-t-butoxycarbonylmethyl-2,3,4,5-tetrahydro-1H-benzazepin-2-one수율 52.2%

시약·촉매·용매 4

HCID 23938Palladium촉매HCID 70681Tetrabutylammonium Chloride촉매HCID 1140Toluene용매HCID 14798Sodium Hydroxide용매

실험 절차

Ethyl 3-benzoylacrylate (13a) (55.6 g, 272 mmoles) is drooped into a solution of (3S)-3-amino-1-t-butoxycarbonylmethyl-2,3,4,5-tetrahydro-1H-benzazepin-2-one (11) (66.2 g, 228 mmoles) in 200 ml of toluene, at room temperature in 1 h. The resulting mixture is left under stirring for 18 h, then a solution of sodium borohydride (228 mmoles 8.6 g) and tetrabutylammonium chloride (5.0 g) in 50 ml of 0.1 M NaOH is added and the mixture is stirred at room temperature for 18 h. The aqueous phase is separated, 50 ml of acetic acid are added to the organic phase and the mixture is left under stirring for 30′, then added with 10% Pd—C (26 g, 22 mmoles) and ammonium formate (456 mmoles, 33.3 g) and left under stirring for 4 h. Afterwards, the catalyst is filtered off through Celite and 100 ml of water is added. The resulting precipitate is filtered, washed with 20 ml of isopropanol and dried to give 3-[[1-(carboxy)-3-phenyl-propyl]amino]-1-t-butoxycarbonylmethyl-2,3,4,5-tetrahydro-1H-benzazepin-2-one (15) (53.9 g, yield: 48%).

후처리

  1. waitThe resulting mixture is left
  2. stirringthe mixture is stirred at room temperature for 18 h
  3. customThe aqueous phase is separated
  4. addition50 ml of acetic acid are added to the organic phase
  5. waitthe mixture is left
  6. stirringunder stirring for 30′,
  7. waitleft
  8. stirringunder stirring for 4 h
  9. filtrationAfterwards, the catalyst is filtered off through Celite and 100 ml of water
  10. additionis added
  11. filtrationThe resulting precipitate is filtered
  12. washwashed with 20 ml of isopropanol
  13. customdried

출처 및 근거

ORD 기록
ord-ea9f74cff65842d7b2d5342fe0badcd9
출처 데이터셋
uspto-grants-2005_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06979736B2

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