Chloroacetyl chloride → HCID 67264695, Verbindung

HRID 1688020Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1688020
Cl[CH2:2][C:3](Cl)=[O:4].[N+:6]([C:9]1[CH:10]=[CH:11][C:12]2[O:18][CH2:17][CH2:16][CH2:15][NH:14][C:13]=2[CH:19]=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:10]=[CH:11][C:12]2[O:18][CH2:17][CH2:16][CH2:15][N:14]([C:3](=[O:4])[CH2:2][N:22]3[CH2:23][CH2:24][CH2:21][CH2:20]3)[C:13]=2[CH:19]=1)([O-:8])=[O:7]

Komponenten

9

Edukt 4

HCID 6577Chloroacetyl chlorideHCID 8471TriethylamineHCID 31268PyrrolidineHCID 109871302,3,4,5-Tetrahydro-7-nitro-1,5-benzoxazepine

Produkt 1

HCID 67264695HCID 67264695, VerbindungAusbeute 88,1 %

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 2-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene (0.58 g, 3.0 mmol;), Triethylamine (1.0 mL, 7.2 mmol), and 4-Dimethylaminopyridine (20 mg, 0.1 mmol; Acros) in Acetonitrile (10 mL) (Exothermic-immediate color change to a dark mixture). The reaction was stirred under an atmosphere of Nitrogen. After 1 h, Pyrrolidine (2.0 mL, 24 mmol) was added, as HPLC had shown the first acylation to be complete. After overnight stirring, 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. The residue was chromatographed (ISCO, 40 g, 0-5% MeOH:DCM) to afford 1-(2-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocyclohepten-9-yl)-2-pyrrolidin-1-yl-ethanone as a yellow oil (807 mg, 88%). 1H-NMR (CDCl3): rotamers, broad spectrum; 13C-NMR (CDCl3): 169.8, 160.3, 142.5, 133.6, 124.8, 124.2, 122.1, 70.9, 57.6, 54.0, 45.3, 28.0, 23.7

Aufarbeitung

  1. stirringAfter overnight stirring
  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. customconc. The residue was chromatographed (ISCO, 40 g, 0-5% MeOH:DCM)

Quellen und Nachweise

ORD-Eintrag
ord-557db2a3a8d249a0ac5c33b9e27c75ce
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08148391B2

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