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

HRID 1041688Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1041688
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]

Komponenten

9

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-1e1d4ad1f02a458892ce9ebc470c5945
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08552186B2

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