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Benzyl chloroformate → (1S,9S)-tert-butyl 9-(benzyloxycarbonylamino)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate

HRID 363857
ノート
印刷プレビュー

反応式

HRID 363857 の反応式
Cl[C:2]([O:4][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[O:3].[NH2:12][C@@H:13]1[C:19](=[O:20])[N:18]2[C@H:21]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])[CH2:22][CH2:23][CH2:24][N:17]2[C:16](=[O:32])[CH2:15][CH2:14]1.C([O-])(O)=O.[Na+].O1CCOCC1>CCOC(C)=O.O>[CH2:5]([O:4][C:2]([NH:12][C@@H:13]1[C:19](=[O:20])[N:18]2[C@H:21]([C:25]([O:27][C:28]([CH3:30])([CH3:29])[CH3:31])=[O:26])[CH2:22][CH2:23][CH2:24][N:17]2[C:16](=[O:32])[CH2:15][CH2:14]1)=[O:3])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 10387Benzyl chloroformateHCID 312751,4-DioxaneHCID 516892Sodium BicarbonateHCID 15434568tert-Butyl (1S,9S)-9-amino-6,10-dioxooctahydro-6H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate

生成物 1

HCID 67022104(1S,9S)-tert-butyl 9-(benzyloxycarbonylamino)-6,10-dioxooctahydro-1H-pyridazino[1,2-a][1,2]diazepine-1-carboxylate収率 88.1%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Benzyl chloroformate (1.07 g) was added dropwise to a stirred ice cold mixture of the (1S, 9S) t-butyl 9-amino-6,10-dioxo-1,2,3,4,7,8,9,10-octahydro-6H-pyridazino[1,2-a][1,2]diazepine-l-carboxylate (GB 2,128,984; 1.55 g, 5.21 mmol), NaHCO3 (0.66 g, 7.82 mmol), dioxan (32 ml) and water (8 ml). The mixture was kept at 5° C. for 15 min then for 2 h at room temperature. The mixture was diluted with EtOAc (50 ml), washed twice with sat. NaHCO3 solution, dried (MgSO4) and concentrated. The oily residue was purified by flash chromatography to afford 211d (1.98 g, 88%) of a colourless oil: [α]D24 -56.4 (c 1.0, CH2Cl2); IR(thin film) 3325, 2979, 2946, 1728, 1677, 1528, 1456, 1422, 1370, 1340, 1272, 1245, 1156, 1122, 1056, 916, 734, 699; 1H NMR (CDCl3) δ7.29 (5H, m), 5.81-5.72 (1H, m), 5.26-5.20 (1H, m), 5.05 (2H, s), 4.69-4.51 (2H, m), 3.48-3.36 (1H, m), 2.81-2.51 (2H, m), 2.34-2.19 (2H, m), 1.90-1.54 (4H, m), 1.41 (9H, s); Anal. Calcd for C22H29N3O6 ·H2O: C, 58.79; H, 6.92; N, 9.35. Found: C, 59.10; H, 6.57; N, 9.25; MS (ES +) 454 (M+ +Na, 87%), 432 (M+ +1, 100).

後処理

  1. waitfor 2 h at room temperature
  2. washwashed twice with sat. NaHCO3 solution
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe oily residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-9926efb6729c417d80e4daa293787975
出典データセット
uspto-grants-1999_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05874424

反応ノート

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