Chloroacetyl chloride → HCID 67264695, Verbindung

HRID 1041678Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1041678
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-aa09566c04fa4a7287bcf5497e13777d
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08552186B2

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