Chloroacetyl chloride → 1-(3-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocyclohepten-9-yl)-2-pyrrolidin-1-yl-ethanone

HRID 1688030ノート

反応式

HRID 1688030 の反応式
Cl[CH2:2][C:3](Cl)=[O:4].[N+:6]([C:9]1[CH:19]=[CH:18][C:12]2[NH:13][CH2:14][CH2:15][CH2:16][O:17][C:11]=2[CH:10]=1)([O-:8])=[O:7].[CH2:20]([N:22](CC)[CH2:23][CH3:24])[CH3:21].N1CCCC1>CN(C)C1C=CN=CC=1.C(#N)C.C(Cl)Cl.O>[N+:6]([C:9]1[CH:19]=[CH:18][C:12]2[N:13]([C:3](=[O:4])[CH2:2][N:22]3[CH2:23][CH2:24][CH2:21][CH2:20]3)[CH2:14][CH2:15][CH2:16][O:17][C:11]=2[CH:10]=1)([O-:8])=[O:7]

参加物

9

反応物 4

HCID 6577Chloroacetyl chlorideHCID 8471TriethylamineHCID 31268PyrrolidineHCID 672641803-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene

生成物 1

HCID 672641431-(3-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocyclohepten-9-yl)-2-pyrrolidin-1-yl-ethanone収率 74%

試薬・触媒・溶媒 4

HCID 142844-(Dimethylamino)pyridine触媒HCID 962Water溶媒HCID 6342Acetonitrile溶媒HCID 6344Dichloromethane溶媒

実験手順

Chloroacetyl chloride (0.50 mL, 6.3 mmol; Acros) was added to a solution of 3-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene (0.580 g, 2.99 mmol), Triethylamine (1.0 mL, 7.2 mmol), and 4-Dimethylaminopyridine (20 mg, 0.1 mmol; Acros) in Acetonitrile (40 mL) The reaction was stirred under an atmosphere of Nitrogen. After 3.5 h, Pyrrolidine (2.0 mL, 24 mmol) was added and stirred overnight. The mixture was diluted with DCM (30 mL) and water (30 mL), the layers separated and the aq. extracted with 10 mL DCM. The combined organics were washed with brine (20 mL) and dried, then conc. onto 4.5 g Celite. The residue was chromatographed (ISCO, 80 g Basic Alumina, 0-70% EtOAc:Hex) to afford 1-(3-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocyclohepten-9-yl)-2-pyrrolidin-1-yl-ethanone as a yellow oil (664 mg, 74%). 1H-NMR (CDCl3): 7.92 (m, 2H), 7.44 (d, 1H, J=8.4 Hz), 4.2-4.6 (m, 4H), 3.15 (m, 2H), 2.48 (m, 4H), 2.10 (m, 2H), 1.70 (m, 4H).

後処理

  1. stirringstirred overnight
  2. customthe layers separated
  3. extractionthe aq. extracted with 10 mL DCM
  4. washThe combined organics were washed with brine (20 mL)
  5. customdried
  6. customThe residue was chromatographed (ISCO, 80 g Basic Alumina, 0-70% EtOAc:Hex)

出典と根拠

ORDレコード
ord-6f7e6093136c438c8d7631427c1c7a3e
出典データセット
uspto-grants-2012_04
特許番号
US08148391B2

反応ノート

読み込み中…